{"id":1654,"date":"2024-08-13T03:29:40","date_gmt":"2024-08-12T19:29:40","guid":{"rendered":"https:\/\/www.homechemer.com\/?p=1654"},"modified":"2025-03-21T05:38:24","modified_gmt":"2025-03-20T21:38:24","slug":"%e4%bd%bf%e7%94%a8pyscf%e7%a8%8b%e5%ba%8f%e5%81%9acasscf%e5%92%8cmc-pdft%e8%ae%a1%e7%ae%97%ef%bc%88%e6%9b%b4%e6%96%b0%e4%b8%ad%ef%bc%89","status":"publish","type":"post","link":"https:\/\/www.homechemer.com\/computchem\/14","title":{"rendered":"\u4f7f\u7528PySCF\u7a0b\u5e8f\u505aCASSCF\u548cMC-PDFT\u8ba1\u7b97\uff08\u66f4\u65b0\u4e2d\uff09"},"content":{"rendered":"\n<p class=\"has-text-align-center\"><strong>\u4f7f\u7528PySCF\u7a0b\u5e8f\u505aCASSCF\u548cMC-PDFT\u8ba1\u7b97<br>CASSCF and MC-PDFT Calculations Using PySCF Program<\/strong><\/p>\n\n\n\n<p class=\"has-text-align-center has-small-font-size\">Jiawei Xu<br>Released: 2024-08-09 \/ Updated: 2024-08-30<\/p>\n\n\n\n<p>MC-PDFT (multi-configuration pair density functional theory)\u662f\u6700\u8fd1\u51e0\u5e74\u9010\u6e10\u5174\u8d77\u7684CASPT2\u548cNEVPT2\u7684\u5e73\u66ff\u65b9\u6cd5\uff0c\u8017\u65f6\u76f8\u6bd4\u540e\u4e24\u8005\u660e\u663e\u964d\u4f4e\uff0c\u4f46\u7cbe\u5ea6\u5374\u635f\u5931\u4e0d\u660e\u663e\uff0c\u76ee\u524d\u4e3b\u8981\u88abOpenMolcas\u3001PySCF-forge\u548cGAMESS\u7b49\u7a0b\u5e8f\u6240\u652f\u6301\u3002\u672c\u6587\u8bb2\u89e3PySCF\u7a0b\u5e8f\u7ed3\u5408PySCF-forge\u6269\u5c55\u5305\u505aMC-PDFT\u8ba1\u7b97\u7684\u57fa\u672c\u65b9\u6cd5\uff0c\u4f46\u7531\u4e8eMC-PDFT\u8ba1\u7b97\u7684\u96be\u70b9\u4e3b\u8981\u662f\u5728CASSCF\u8ba1\u7b97\u90e8\u5206\uff0c\u6545\u672c\u6587\u5b9e\u9645\u4e0a\u91cd\u70b9\u8bb2\u89e3PySCF\u505aCASSCF\u8ba1\u7b97\u7684\u65b9\u6cd5\uff0c\u90e8\u5206\u6d41\u7a0b\u4f1a\u4f7f\u7528\u5230MOKIT\u7a0b\u5e8f\u4f5c\u4e3a\u534f\u52a9\u3002<\/p>\n\n\n\n<p><strong>1. \u79bb\u7ebf\u5b89\u88c5PySCF\u548cPySCF-forge\u6269\u5c55\u5305<\/strong><\/p>\n\n\n\n<p>\u5bf9\u4e8e\u6709root\u6743\u9650\u3001\u5728\u7ebf\u5b89\u88c5\u7684\u60c5\u51b5\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">pip install pyscf<br>pip install pyscf-forge<\/code><\/pre>\n\n\n\n<p>\u5bf9\u4e8e\u6700\u4e00\u822c\u7684\u3001\u65e0root\u6743\u9650\u3001\u79bb\u7ebf\u5b89\u88c5\u7684\u60c5\u51b5\uff0c\u63a8\u8350\u4f7f\u7528Anaconda Python\u3002\u9996\u5148\u5728\u4e00\u53f0\u80fd\u8054\u7f51\u7684\u673a\u5b50\u4e0a\u5b89\u88c5\u4e0e\u96c6\u7fa4\u76f8\u8fd1\u7248\u672c\u7684Anaconda Python\uff0c\u5e76\u4e0b\u8f7dPySCF\u53ca\u5176\u5fc5\u8981\u4f9d\u8d56\u7684\u5b89\u88c5\u5305\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">pip download pyscf<br>pip download pyscf-forge<\/code><\/pre>\n\n\n\n<p>\u4e0a\u8ff0\u547d\u4ee4\u5c06\u4f1a\u4e0b\u8f7d\u5f97\u5230\u4e00\u7cfb\u5217\u7684.whl\u5b89\u88c5\u5305\uff0c\u5c06\u4e4b\u4e0a\u4f20\u81f3\u96c6\u7fa4\u3002\u6211\u4eec\u9009\u62e9\u4f7f\u7528Anaconda Python\uff0c\u7531\u4e8ePySCF\u662f\u6bd4\u8f83\u5e38\u7528\u7684\u5e93\uff0c\u53ef\u4ee5\u76f4\u63a5\u5b89\u88c5\u5728base\u73af\u5883\u3002\u9996\u5148\u6fc0\u6d3bbase\u73af\u5883\uff0c\u7136\u540e\u4f7f\u7528pip\u5b89\u88c5\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">source ~\/programs\/Anaconda3\/bin\/activate base<br>which pip # \u786e\u8ba4pip\u8def\u5f84\uff0c\u6b64\u65f6\u5e94\u5bf9\u5e94\u4e8e~\/programs\/Anaconda3\/bin\/pip\uff0c\u9ed8\u8ba4\u5b89\u88c5\u81f3~\/programs\/Anaconda3\/lib\/python3.X\/site-packages<br>pip install pyscf-2.xxx.whl<\/code><\/pre>\n\n\n\n<p><strong>2. \u7b80\u5355CASSCF\u8ba1\u7b97<\/strong><\/p>\n\n\n\n<p><strong>2.1 \u82ef<\/strong><br>\u82ef\u5206\u5b50\u57fa\u6001\u7684\u6d3b\u6027\u7a7a\u95f4\u4e00\u822c\u9009\u4e3a(6o,6e)\uff0c\u5373\u5305\u542b\u5168\u90e86\u4e2a\u03c0\u8f68\u9053\u548c6\u4e2a\u03c0\u7535\u5b50\u3002\u8be5\u8ba1\u7b97\u53ef\u76f4\u63a5\u4f7f\u7528MOKIT\u4e2d\u7684automr\u7a0b\u5e8f\u5168\u81ea\u52a8\u5b8c\u6210\uff0c\u8f93\u5165\u6587\u4ef6\u5982\u4e0b\uff08\u539f\u5b50\u5750\u6807\u7565\uff09\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">%nprocshared=28<br>%mem=84GB<br>#p CASSCF\/def2SVP<br><br>mokit{}<br><br>0 1<br>[Cartesian Coordinates]<\/code><\/pre>\n\n\n\n<p>\u6ce8\u610f\uff1adef2-SVP\u57fa\u7ec4\u5bf9\u4e8eCASSCF\u8ba1\u7b97\u800c\u8a00\u592a\u7c97\u7cd9\uff0c\u6b64\u5904\u4ec5\u4f5c\u4e3a\u6f14\u793a\u65f6\u4f7f\u7528\uff0c\u8be5\u4efb\u52a1\u4e0d\u5230\u4e00\u5206\u949f\u5c31\u80fd\u8fc5\u901f\u7b97\u5b8c\u3002<br>\u82ef\u5206\u5b50\u6bd4\u8f83\u7b80\u5355\uff0c\u6240\u4ee5\u4f7f\u7528\u9ed8\u8ba4\u7684\u8bbe\u7f6e\u5373\u53ef\u3002MOKIT\u4f1a\u9996\u5148\u5bf9\u6240\u63d0\u4f9b\u7ed3\u6784\u8fdb\u884cRHF\u548cUHF\u8ba1\u7b97\uff0c\u5e76\u6839\u636e\u80fd\u91cf\u5224\u65ad\u4f53\u7cfb\u4e3a\u95ed\u58f3\u5c42\u6216\u5f00\u58f3\u5c42\u3002\u5bf9\u4e8e\u95ed\u58f3\u5c42\u7684\u60c5\u51b5\uff0c\u4f1a\u9996\u5148\u5bf9\u865a\u8f68\u9053\u8fdb\u884c\u6295\u5f71\uff0c\u7136\u540e\u505a\u5b9a\u57df\u5316\uff0c\u5e76\u5339\u914d\u6210\u952e\u548c\u53cd\u952e\u8f68\u9053\u3002\u5bf9\u4e8e\u5f00\u58f3\u5c42\u7684\u60c5\u51b5\u5219\u662f\u57fa\u4e8eUHF\u6ce2\u51fd\u6570\u5f97\u5230UNO (unrestricted natural orbital)\uff0c\u7136\u540e\u5339\u914d\u6210\u952e\u548c\u53cd\u952e\u8f68\u9053\u3002\u57fa\u4e8e\u6b64\uff0c\u8c03\u7528GAMESS\uff08\u6216Gaussian\uff09\u505a\u5e7f\u4e49\u4ef7\u952e\u8ba1\u7b97(generalized valence bond, GVB)\uff0c\u5e76\u5c06\u6536\u655b\u7684GVB\u6ce2\u51fd\u6570\u4f5c\u9002\u5f53\u5904\u7406\u9009\u51fa\u6d3b\u6027\u7a7a\u95f4\uff0c\u4f20\u9012\u7ed9PySCF\u8fdb\u884cCASSCF\u8ba1\u7b97\u3002\u672c\u4f8bMOKIT\u81ea\u52a8\u9009\u51fa\u7684\u6d3b\u6027\u7a7a\u95f4\u5373\u4e3a(6o,6e)\uff0c\u8ba1\u7b97\u5b8c\u6210\u540e\u5f97\u5230\u4e00\u7cfb\u5217\u7684\u8f93\u51fa\u6587\u4ef6\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"303\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5-1024x303.png\" alt=\"\" class=\"wp-image-1668\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5-1024x303.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5-300x89.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5-768x227.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5-1536x454.png 1536w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5-583x172.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-5.png 1904w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u89c2\u5bdfph_uhf_gvb15_CASSCF_NO.fch\u4e2d\u7684\u8f68\u9053\uff0c\u53ef\u89c1\u6d3b\u6027\u7a7a\u95f4\u5185\u7684NO\u5747\u4e3a\u975e\u6574\u6570\u5360\u636e\uff0c\u603b\u5360\u636e\u6570\u4e3a6\uff0c\u5176\u7b49\u503c\u9762\u56fe\u50cf\u4e5f\u7b26\u5408\u82ef\u73af\u03c0\u8f68\u9053\u7684\u56fe\u50cf\uff1a<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"315\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-4-1024x315.png\" alt=\"\" class=\"wp-image-1666\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-4-1024x315.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-4-300x92.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-4-768x236.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-4-583x179.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-4.png 1478w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u6211\u4eec\u7b80\u5355\u8bb2\u89e3\u4e00\u4e9b\u6709\u5173\u8f68\u9053\u81ea\u52a8\u9009\u62e9\u7684\u8ba1\u7b97\u7ec6\u8282\u3002\u76f8\u6bd4\u4e8eFull CI\uff0cCASSCF\u5b9e\u9645\u4e0a\u662f\u9009\u62e9\u4e00\u90e8\u5206\u6700\u5177\u5316\u5b66\u610f\u4e49\u7684\u8f68\u9053\u548c\u7535\u5b50\u4f5c\u4e3a\u6d3b\u6027\u7a7a\u95f4\uff0c\u5728\u6d3b\u6027\u7a7a\u95f4\u8303\u56f4\u5185\u505aFull CI\u3002\u4e0e\u4e4b\u7c7b\u4f3c\uff0cGVB\u5b9e\u9645\u4e0a\u4e5f\u662f\u9488\u5bf9\u4e00\u90e8\u5206\u6210\u53cd\u952e\u8f68\u9053\u5bf9\u8fdb\u884c\u6709\u9650\u8303\u56f4\u5185\u7684VB\u8ba1\u7b97\uff0c\u56e0\u6b64GVB\u8f68\u9053\u5bf9\u4e5f\u53ef\u4ee5\u770b\u505a\u662f\u67d0\u79cd\u610f\u4e49\u4e0a\u7684\u6d3b\u6027\u7a7a\u95f4\u3002<br>\u5728\u7531UNO\u5411GVB\u4f20\u9012\u521d\u731c\u65f6\uff0cMOKIT\u9ed8\u8ba4\u9009\u62e9\u5360\u636e\u6570\u8d85\u8fc710<sup>-5<\/sup>\u7684\u7a7a\u8f68\u9053\uff0c\u4e5f\u5373ph_uhf_uno_asrot.fch\u4e2d\u768422~36\u53f7\u8f68\u9053\uff0c\u5c06\u5176\u4ee5\u53ca\u4e0e\u5176\u4e00\u4e00\u5bf9\u5e94\u76847~21\u53f7\u5360\u636e\u8f68\u9053\u5168\u90e8\u7eb3\u5165GVB\u6d3b\u6027\u7a7a\u95f4\uff0c\u517115\u5bf9GVB\u8f68\u9053\u5bf9\uff0c\u6545\u540e\u7eed\u6587\u4ef6\u547d\u540d\u4f7f\u7528&#8221;gvb15&#8243;\u3002\u8fd9\u4e2a\u6807\u51c6\u5f88\u4e25\u683c\uff0c\u7edd\u5927\u591a\u6570\u60c5\u51b5\u4e0b\u5b9e\u9645\u4e0a\u5df2\u7ecf\u5305\u542b\u4e86\u6240\u6709\u7684\u4ef7\u5c42\u8f68\u9053\u3002\u8fd9\u4e2a\u9608\u503c\u53ef\u4ee5\u901a\u8fc7\u5173\u952e\u8bcd\u4fee\u6539\uff0c\u5982<mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-1-color\">uno_thres=0.001<\/mark>\u5219\u4f1a\u5c06\u6b64\u6807\u51c6\u653e\u5bbd\u81f30.001\u3002\u5982\u679c\u91c7\u75280.001\u7684\u9608\u503c\uff0cGVB\u8ba1\u7b97\u5c06\u4ec5\u9650\u4e8e\u03c0\u8f68\u9053\uff0c\u5373ph_uhf_uno_asrot.fch\u4e2d\u768419~24\u53f7\u8f68\u9053\uff0c\u5bf9\u4e8e\u672c\u4f8b\u6765\u8bf4\u5b9e\u9645\u4e0a\u5f71\u54cd\u4e0d\u5927\uff0c\u56e0\u4e3a\u82ef\u73af\u4ef7\u5c42\u8f68\u9053\u4e2d\u7684\u5176\u4ed6C-C C-H \u03c3\u8f68\u9053\u672c\u8eab\u591a\u53c2\u8003\u6027\u5c31\u51e0\u4e4e\u53ef\u4ee5\u5ffd\u7565\u3002\u6b64\u5916\uff0c\u4e5f\u53ef\u4ee5\u901a\u8fc7<mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-1-color\">excludeXH<\/mark>\u5173\u952e\u8bcd\u76f4\u63a5\u53bb\u9664GVB\u8ba1\u7b97\u4e2d\u7684C-H\u952e\u8f68\u9053\u3002<br>\u7c7b\u4f3c\u5730\uff0c\u5728\u7531GVB\u5411CASSCF\u4f20\u9012\u521d\u731c\u65f6\uff0c\u4e5f\u662f\u901a\u8fc7\u5360\u636e\u6570\u51b3\u5b9a\u6d3b\u6027\u7a7a\u95f4\u6240\u5305\u542b\u7684\u8f68\u9053\u8303\u56f4\u3002MOKIT\u9ed8\u8ba4\u5c06\u5360\u636e\u6570\u57280.02~1.98\u8303\u56f4\u5185\u7684\u8f68\u9053\u5168\u90e8\u7eb3\u5165\u8003\u8651\uff0c\u4f46\u8fd9\u4e00\u8303\u56f4\u6ca1\u6709\u73b0\u6210\u7684\u5173\u952e\u8bcd\u53ef\u4ee5\u4fee\u6539\uff08\u81f3\u5c11\u5bf9\u4e8e\u64b0\u6587\u65f6\u662f\u5982\u6b64\uff09\u3002\u8fd9\u5c31\u5bf9\u5e94\u4e8eph_uhf_uno_asrot2gvb15_s.fch\u4e2d\u768419~24\u53f7\u8f68\u9053\uff0c\u6070\u597d\u662f\u6240\u6709\u7684\u03c0\u8f68\u9053\u3002\u4e5f\u53ef\u4ee5\u5728GVB\u5b8c\u6210\u540e\u7ec8\u6b62\u8ba1\u7b97\uff0c\u5e76\u901a\u8fc7\u5173\u952e\u8bcd<mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-1-color\">on_thresh=0.01,readno=&#8221;ph_uhf_uno_asrot2gvb15_s.fch&#8221;,ist=5<\/mark>\u4ee5NO\u7684\u5f62\u5f0f\u8bfb\u53d6GVB\u6ce2\u51fd\u6570\uff0c\u5e76\u53d60.01\u4f5c\u4e3a\u5360\u636e\u6570\u504f\u79bb0\u548c2\u7684\u9608\u503c\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"567\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3-1024x567.png\" alt=\"\" class=\"wp-image-1664\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3-1024x567.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3-300x166.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3-768x425.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3-1536x850.png 1536w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3-542x300.png 542w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-3.png 1624w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p><strong>2.2 \u82ef\u915a<\/strong><br>\u4ec5\u8003\u8651\u82ef\u7684\u90e8\u5206\uff0c\u6d3b\u6027\u7a7a\u95f4\u4ecd\u4e3a(6o,6e)\uff0c\u4f46\u8003\u8651\u5230\u6c27\u539f\u5b50\u7684LP\u7535\u5b50\u4f1a\u4e0e\u03c0\u952e\u4ea7\u751f\u4e00\u5b9a\u7a0b\u5ea6\u7684\u5171\u8f6d\uff0c\u9009\u62e9(7o,8e)\u7684\u6d3b\u6027\u7a7a\u95f4\u4f3c\u4e4e\u66f4\u59a5\u3002\u4f46\u7531\u4e8eMOKIT\u7a0b\u5e8f\u662f\u6210\u5bf9\u5730\u6784\u5efa\u521d\u731c\u6ce2\u51fd\u6570\uff0c\u56e0\u6b64\u5b9e\u9645\u4e0a\u53ea\u80fd\u8ba1\u7b97\u6d3b\u6027\u8f68\u9053\u6570\u548c\u6d3b\u6027\u7535\u5b50\u6570\u76f8\u7b49\uff0c\u5373(no,ne)\u7684\u60c5\u51b5\uff0c\u56e0\u6b64\u4e0d\u53ef\u80fd\u9009\u51fa(7o,8e)\u7684\u6d3b\u6027\u7a7a\u95f4\u3002\u6211\u4eec\u9996\u5148\u4eff\u7167<strong>2.1<\/strong>\u4e2d\u505a\u6cd5\u4f7f\u7528MOKIT\u7a0b\u5e8f\u81ea\u52a8\u505aCASSCF\u8ba1\u7b97\uff0c\u53ef\u4ee5\u770b\u5230\u6240\u9009\u51fa\u7684\u6d3b\u6027\u7a7a\u95f4\u4ecd\u4e3a(6o,6e)\uff0c\u5305\u542b23~28\u53f7\u8f68\u9053\uff0c\u800c\u6c27\u539f\u5b50\u7684LP\u8f68\u9053\u4e3a20\u53f7\u8f68\u9053\uff0c\u4e0d\u5728\u6d3b\u6027\u7a7a\u95f4\u7684\u8303\u56f4\u5185\u3002\u8fd9\u662f\u7531\u4e8e\u5728GVB\u8ba1\u7b97\u7ed3\u679c\u4e2d\uff0c\u6c27\u539f\u5b50LP\u8f68\u9053\u7684\u5360\u636e\u6570\u4e0d\u5728\u9ed8\u8ba4\u76840.02~1.98\u8303\u56f4\u5185\uff0c\u56e0\u6b64\u88ab\u6392\u9664\u51fa\u4e86\u6d3b\u6027\u7a7a\u95f4\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"135\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-6-1024x135.png\" alt=\"\" class=\"wp-image-1676\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-6-1024x135.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-6-300x40.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-6-768x101.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-6-583x77.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-6.png 1526w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u6211\u4eec\u5f53\u7136\u53ef\u4ee5\u8bfb\u53d6GVB\u6ce2\u51fd\u6570\uff0c\u5e76\u901a\u8fc7on_thresh\u6765\u8c03\u6574\u6d3b\u6027\u7a7a\u95f4\u7684\u8303\u56f4\uff0c\u4f46\u8fd9\u4f1a\u540c\u65f6\u8003\u8651\u4e0d\u5fc5\u8981\u7684\u5176\u4ed6\u4e00\u4e9b\u8f68\u9053\uff0c\u589e\u5927\u8ba1\u7b97\u91cf\u3002\u8fd9\u65f6\u5019\u5c31\u9700\u8981\u4eba\u4e3a\u5730\u8c03\u6574\u8f68\u9053\u987a\u5e8f\u3002\u9996\u5148\u6211\u4eec\u8981\u7406\u89e3PySCF\u7684\u8f93\u5165\u6587\u4ef6\u4e2d\u5982\u4f55\u5b9a\u4e49\u6d3b\u6027\u7a7a\u95f4\uff1amcscf.CASSCF(m,(na,nb))\u8868\u793a\u6d3b\u6027\u7a7a\u95f4\u5305\u542bm\u4e2a\u7a7a\u95f4\u8f68\u9053\uff0cna\u4e2a\u03b1\u7535\u5b50\u548cnb\u4e2a\u03b2\u7535\u5b50\uff0c\u6b64\u65f6\u6d3b\u6027\u7a7a\u95f4\u5b9e\u9645\u4e0a\u662f\u5305\u542b\u4e86\u524d\u7ebf\u8f68\u9053\u9644\u8fd1\u7684\u8fd9\u90e8\u5206\u8f68\u9053\u548c\u7535\u5b50\u3002\u5bf9\u4e8e\u5355\u91cd\u6001\u7684\u82ef\u915a\uff0cmcscf.CASSCF(6,(3,3))\u5c31\u5bf9\u5e94\u4e8eHOMO-2\u3001HOMO-1\u3001HOMO\u3001LUMO\u3001LUMO+1\u548cLUMO+2\u53ca3\u4e2a\u03b1\u7535\u5b50\u548c3\u4e2a\u03b2\u7535\u5b50\u3002\u56e0\u6b64\uff0c\u989d\u5916\u5305\u542b\u6c27\u539f\u5b50\u7684LP\u8f68\u9053\u540e\uff0c\u6d3b\u6027\u7a7a\u95f4\u7684\u5b9a\u4e49\u53d8\u4e3amcscf.CASSCF(7,(4,4))\uff0c\u540c\u65f6\u6211\u4eec\u8fd8\u9700\u8981\u5c0620\u53f7\u8f68\u9053\u4e0e22\u53f7\u8f68\u9053\u8c03\u6362\u987a\u5e8f\uff0c\u884c\u5217\u5f0f\u6ce2\u51fd\u6570\u7684\u6027\u8d28\u51b3\u5b9a\u4e86\u8c03\u6362\u8f68\u9053\u987a\u5e8f\u4ec5\u6539\u53d8\u7b26\u53f7\uff0c\u800c\u4e0d\u6539\u53d8\u6ce2\u51fd\u6570\u5176\u4ed6\u6027\u8d28\u3002\u4f7f\u7528Multiwfn\u7684\u4e3b\u529f\u80fd6\u8c03\u6362\u987a\u5e8f\uff0c\u5e76\u5c06\u5176\u91cd\u65b0\u4fdd\u5b58\u4e3aexchanged.fch\u6587\u4ef6\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">Multiwfn phenol_uhf_gvb16_CASSCF_NO.fch<br>6<br>29<br>20,22<br>-1<br>100<br>2<br>7<br>exchanged.fch<br>0<br>q<\/code><\/pre>\n\n\n\n<p>\u6d4b\u8bd5\u8868\u660e\uff0cMultiwfn\u751f\u6210\u7684\u8fd9\u4e2afch\u6587\u4ef6\u5e76\u4e0d\u80fd\u88abPySCF\u6b63\u786e\u8bfb\u53d6\uff0c\u786e\u5207\u5730\u8bf4\u662f\u4e0d\u80fd\u88abPySCF\u8f93\u5165\u6587\u4ef6\u4e2d\u6240\u8c03\u7528\u7684MOKIT\u4e2d\u63d0\u4f9b\u7684fch2py\u51fd\u6570\u6b63\u786e\u8bfb\u53d6\u3002\u65e0\u59a8\uff0c\u6211\u4eec\u53ef\u4ee5\u7528Gaussian\u6574\u7406\u5176\u6587\u4ef6\u683c\u5f0f\uff0c\u5148\u8f6c\u6362\u4e3a.chk\u683c\u5f0f\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">unfchk exchanged.fch exchanged.chk<\/code><\/pre>\n\n\n\n<p>\u7f16\u5199\u5982\u4e0bGaussian\u8f93\u5165\u6587\u4ef6\uff0c\u5e76\u8fd0\u884c\u4e4b\uff0c\u8be5\u4efb\u52a1\u4f1a\u8fc5\u901f\u5b8c\u6210\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">%chk=exchanged.chk<br>#p ROHF\/def2SVP guess=(read,only) geom=allchk nosymm int=nobasistransform<\/code><\/pre>\n\n\n\n<p>\u6ce8\u610f\u4e0a\u8ff0\u4efb\u52a1\u9700\u8981\u4fdd\u6301\u57fa\u7ec4\u4e0e\u6b64\u524d\u7684\u8ba1\u7b97\u5747\u4e00\u81f4\u3002\u5f97\u5230\u65b0\u7684.chk\u6587\u4ef6\u540e\uff0c\u518d\u8f6c\u6362\u4e3a.fch\u683c\u5f0f\u5373\u53ef\uff0c\u6b64\u65f6\u6211\u4eec\u5c31\u5f97\u5230\u4e86\u4e00\u4e2a\u53ef\u4ee5\u6b63\u786e\u88abpy2fch\u8bfb\u53d6\u7684.fch\u6587\u4ef6\u4f5c\u4e3a\u521d\u731c\u4e86\u3002\u7531\u4e8e\u524d\u9762\u5df2\u7ecf\u8fdb\u884c\u8fc7\u6d3b\u6027\u7a7a\u95f4(6o,6e)\u7684CASSCF\u8ba1\u7b97\uff0c\u56e0\u6b64\u5b9e\u9645\u4e0a\u53ea\u9700\u8981\u57fa\u4e8e\u6b64\u524d\u7684PySCF\u8f93\u5165\u6587\u4ef6\u4fee\u6539\u6d3b\u6027\u7a7a\u95f4\u5b9a\u4e49\u548c\u521d\u731c\u6ce2\u51fd\u6570\u6587\u4ef6\u540d\u5373\u53ef\u3002\u6267\u884c\u8be5\u6d3b\u6027\u7a7a\u95f4(7o,8e)\u7684CASSCF\u8ba1\u7b97\uff0c\u89c2\u5bdf\u6240\u5f97\u6ce2\u51fd\u6570\u5c31\u4f1a\u53d1\u73b0\uff0c\u6c27\u539f\u5b50\u7684LP\u8f68\u9053\u76f8\u8f83\u4e8e\u7eb3\u5165\u6d3b\u6027\u7a7a\u95f4\u524d\u53d1\u751f\u4e86\u660e\u663e\u7684\u53d8\u5316\uff0c\u800c\u5176\u4ed6\u03c0\u8f68\u9053\u4e5f\u7531\u4e8e\u5171\u8f6d\u90fd\u63ba\u5165\u4e86\u4e00\u5b9aLP\u8f68\u9053\u7684\u6210\u5206\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"142\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-7-1024x142.png\" alt=\"\" class=\"wp-image-1678\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-7-1024x142.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-7-300x42.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-7-768x107.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-7-583x81.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-7.png 1520w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u6bd4\u8f83\u4e24\u6b21\u8ba1\u7b97\u5f97\u5230\u7684CASSCF\u80fd\u91cf\uff1aCASSCF(6,6) -305.406703386517 a.u.\uff1bCASSCF(7,8) -305.407351500871 a.u. \u53ef\u89c1\u6269\u5927\u6d3b\u6027\u7a7a\u95f4\u540e\u80fd\u91cf\u6709\u6240\u964d\u4f4e\uff0c\u4f46\u7531\u4e8eLP\u8f68\u9053\u4e0e\u03c0\u8f68\u9053\u7684\u5171\u8f6d\u7a0b\u5ea6\u8f83\u5c0f\uff0c\u80fd\u91cf\u5dee\u5f02\u5e76\u4e0d\u660e\u663e\u3002\u4e00\u822c\u6765\u8bf4\uff0c\u90fd\u8981\u6c42\u6d3b\u6027\u7a7a\u95f4\u7684\u5927\u5c0f\u76f8\u540c\u65f6\u624d\u53ef\u4ee5\u6bd4\u8f83\u80fd\u91cf\u3002\u4e5f\u53ef\u4ee5\u67e5\u770bCASSCF(7,8)\u8ba1\u7b97\u7684\u7b2c\u4e00\u8f6e\u8fed\u4ee3\u7684\u80fd\u91cf\uff0c\u5373\u521d\u731c\u6ce2\u51fd\u6570CASCI\u7684\u80fd\u91cf\u4e3aE0 = -305.407324890267 a.u.\uff0c\u8fd9\u5c31\u6307\u660e\u4e86\u540c\u4e00\u6ce2\u51fd\u6570\u5728\u4e0d\u540c\u6d3b\u6027\u7a7a\u95f4\u4e0b\u6240\u5f97\u7684\u80fd\u91cf\u662f\u4e0d\u53ef\u6bd4\u8f83\u7684\u3002\u540c\u65f6\uff0cE0\u4e0eCASSCF(7,8)\u6700\u7ec8\u6536\u655b\u7684\u80fd\u91cf\u4e4b\u95f4\u7684\u5dee\u503c\u4e5f\u53ef\u4ee5\u770b\u505a\u662f\u7531LP\u8f68\u9053\u4e0e\u03c0\u8f68\u9053\u5171\u8f6d\u6240\u5e26\u6765\u7684\u80fd\u91cf\u964d\u4f4e\u3002<\/p>\n\n\n\n<hr class=\"wp-block-separator has-alpha-channel-opacity is-style-wide\"\/>\n\n\n\n<p><strong><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-1-color\">\u4f7f\u7528MOKIT\u8c03\u6362\u8f68\u9053\u987a\u5e8f<br><\/mark><\/strong>MOKIT\u6709\u4e00\u5185\u7f6e\u7684<a href=\"https:\/\/jeanwsr.gitlab.io\/mokit-doc-mdbook\/chap4-6.html#4614-permute_orb\" target=\"_blank\" rel=\"noreferrer noopener\">permute_orb<\/a>\u51fd\u6570\u4e5f\u53ef\u7528\u4e8e\u8c03\u6362\u8f68\u9053\u3002\u7f16\u5199\u4e00\u4e2apython\u6587\u4ef6\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">from mokit.lib.gaussian import permute_orb<br>permute_orb('ethanol_rhf_proj_loc_pair2gvb8_s.fch',6,13)<\/code><\/pre>\n\n\n\n<p>\u8fd0\u884c\u5373\u53ef\u8c03\u6362\u6307\u5b9a\u6587\u4ef6\u4e2d\u4e24\u4e2a\u8f68\u9053\u7684\u987a\u5e8f\uff0c\u8f68\u9053\u7f16\u53f7\u4ece1\u5f00\u59cb\u3002\u4e5f\u53ef\u4ee5\u5c06\u6b64\u76f4\u63a5\u5199\u8fdbPySCF\u505aCASSCF\u8ba1\u7b97\u7684\u8f93\u5165\u6587\u4ef6\u3002<\/p>\n\n\n\n<hr class=\"wp-block-separator has-alpha-channel-opacity is-style-wide\"\/>\n\n\n\n<p><strong>2.3 \u4e8c\u8302\u94c1<\/strong><br>\u5728PBE0-D3(BJ)\/def2-SVP\u4e0b\u4f18\u5316\u5f97\u5230\u4e8c\u8302\u94c1\u7684\u6781\u5c0f\u70b9\u7ed3\u6784\uff0c\u5e76\u4f7f\u7528MOKIT\u505a\u9ed8\u8ba4\u7684CASSCF\u8ba1\u7b97\uff0c\u5c06\u5f97\u5230\u4ee5\u4e0b\u7ed3\u679c\u3002\u8fd9\u662f\u7531\u4e8e\u5728\u6536\u655b\u6240\u5f97\u7684GVB\u6ce2\u51fd\u6570\u4e2d\u5e76\u6ca1\u6709\u5360\u636e\u6570\u4ecb\u4e8e0.02~1.98\u4e4b\u95f4\u7684\u8f68\u9053\uff0c\u56e0\u6b64\u6ca1\u6709\u8f68\u9053\u88ab\u9009\u5165\u6d3b\u6027\u7a7a\u95f4\u3002\u4e00\u822c\u6765\u8bf4\uff0c\u8fd9\u8868\u660e\u5f53\u524d\u8ba1\u7b97\u7684\u4f53\u7cfb\u591a\u53c2\u8003\u6027\u8f83\u5f31\uff0c\u4f7f\u7528CASSCF\u8ba1\u7b97\u7684\u610f\u4e49\u4e0d\u5927\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-full\"><img loading=\"lazy\" decoding=\"async\" width=\"747\" height=\"256\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/d3337f8868f4ebb4dcc5bb0fcdb71973.png\" alt=\"\" class=\"wp-image-1686\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/d3337f8868f4ebb4dcc5bb0fcdb71973.png 747w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/d3337f8868f4ebb4dcc5bb0fcdb71973-300x103.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/d3337f8868f4ebb4dcc5bb0fcdb71973-583x200.png 583w\" sizes=\"auto, (max-width: 747px) 100vw, 747px\" \/><\/figure>\n<\/div>\n\n\n<p>\u5373\u4fbf\u5982\u6b64\uff0c\u6211\u4eec\u4e5f\u4f9d\u7136\u53ef\u4ee5\u4f7f\u7528CASSCF\u65b9\u6cd5\u8ba1\u7b97\u4e8c\u8302\u94c1\u7684\u7535\u5b50\u7ed3\u6784\uff0c\u6700\u7406\u60f3\u7684\u6d3b\u6027\u7a7a\u95f4\u5e94\u5f53\u5305\u542bFe\u7684\u5168\u90e85\u4e2a3d\u8f68\u9053\uff0c\u4ee5\u53ca\u4e24\u4e2a\u73af\u620a\u4e8c\u70ef\u8d1f\u79bb\u5b50\u768410\u4e2a\u03c0\u8f68\u9053\uff0c\u603b\u5171\u670918\u4e2a\u7535\u5b50\u5360\u636e\uff0c\u5219\u6d3b\u6027\u7a7a\u95f4\u7684\u5927\u5c0f\u4e3a(15o,18e)\u3002\u9996\u5148\u901a\u8fc7\u89c2\u5bdfGVB\u8f68\u9053\u7684\u56fe\u50cf\u786e\u8ba4\u8fd915\u4e2a\u8f68\u9053\u7684\u5e8f\u53f7\uff0c\u5982\u4e0b\u56fe\u6240\u793a\u3002\u5982\u4f55\u8fc5\u901f\u9009\u4e2d\u8fd9\u4e9b\u8f68\u9053\uff0c\u8fd9\u91cc\u5c31\u672c\u4f8b\u800c\u8a00\u8c08\u4e00\u79cd\u7b56\u7565\uff1a<br>\u2460 22~24\u53f7\u8f68\u9053\u662fFe\u76843d<sup>6<\/sup>\u8f68\u9053\uff0c\u4ece\u914d\u4f53\u573a\u7406\u8bba(ligand field theory, LFT)\u7684\u89d2\u5ea6\u800c\u8a00\uff0c\u8fd9\u4e09\u4e2ad\u8f68\u9053\u4e0d\u4e0e\u914d\u4f53\u7684\u8f68\u9053\u53d1\u751f\u6df7\u5408\uff0c\u56e0\u6b64\u8868\u73b0\u4e3aLP\u8f68\u9053\uff0c\u56e0\u800c\u4e5f\u6613\u4e8e\u4ece\u56fe\u50cf\u76f4\u63a5\u8fa8\u8ba4\u3002<br>\u2461 36\/46\/48\u548c35\/37\/47\u5206\u522b\u662f\u4e0a\u4e0b\u4e24\u4e2a\u73af\u620a\u4e8c\u70ef\u8d1f\u79bb\u5b50\u7684\u03c0\u8f68\u9053\u3002<br>\u2462 \u6839\u636e\u4ef7\u952e\u7406\u8bba\u7684\u601d\u60f3\uff0c\u6bcf\u4e2a\u6210\u952e\u8f68\u9053\u90fd\u5e94\u5bf9\u5e94\u4e8e\u4e00\u4e2a\u53cd\u952e\u8f68\u9053\uff0c\u76f8\u5e94\u5730\u5c31\u670949\/51\/61\u548c50\/60\/62\u4e3a\u5176\u53cd\u952e\u8f68\u9053\uff0c\u56e0\u4e3a\u5728MOKIT\u5904\u7406\u8fc7\u7684GVB\u6ce2\u51fd\u6570\u4e2d\uff0c\u8f68\u9053\u6309\u5360\u636e\u6570\u6392\u5e8f\uff0c\u56e0\u800c\u6210\u53cd\u952e\u8f68\u9053\u7684\u5e8f\u53f7\u6070\u597d\u662f\u5173\u4e8eHOMO-LUMO (48-49)\u5bf9\u79f0\u5206\u5e03\u7684\u3002\u4f46\u8fd9\u5c31\u4f1a\u4ea7\u751f12\u4e2a\u03c0\/\u03c0*\u8f68\u9053\uff0c\u8fd9\u662f\u4e0d\u7b26\u5408\u5e38\u7406\u7684\u3002\u5b9e\u9645\u4e0a\u8fd9\u91cc\u76846\u4e2a\u201c\u03c0\u8f68\u9053\u201d\u5df2\u7ecf\u4e0d\u662f\u5355\u7eaf\u7684\u03c0\u8f68\u9053\uff0c\u800c\u662f\u975e\u5360\u636ed\u8f68\u9053\u548c\u03c0\u8f68\u9053\u76f8\u4e92\u4f5c\u7528\u4ea7\u751f\u7684\u6210\u952e\u8f68\u9053\uff0c\u53cd\u952e\u8f68\u9053\u4f3c\u6b64\uff0c\u53ea\u4e0d\u8fc7\u90e8\u5206\u8f68\u9053\u4ecd\u7136\u5f88\u5927\u7a0b\u5ea6\u4e0a\u4fdd\u7559\u4e86\u03c0\/\u03c0*\u8f68\u9053\u7684\u56fe\u50cf\uff0c\u5373\u53ea\u670936\/61\u548c35-62\u4e24\u7ec4\u6709\u660e\u663e\u7684d-\u03c0\u56fe\u50cf\u6027\u8d28\u3002\u5177\u4f53\u53ef\u53c2\u8003\u914d\u4f53\u573a\u7406\u8bba\u4ee5\u53ca\u7fa4\u8bba\u7684\u5185\u5bb9\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"358\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-12-1024x358.png\" alt=\"\" class=\"wp-image-1914\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-12-1024x358.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-12-300x105.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-12-768x269.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-12-583x204.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-12.png 1224w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u503c\u5f97\u4e00\u63d0\u7684\u662f\uff0cGVB\u6ce2\u51fd\u6570\u4e2d\u73af\u620a\u4e8c\u70ef\u8d1f\u79bb\u5b50\u7684\u03c0\u8f68\u9053\u5e76\u4e0d\u662f\u4f20\u7edf\u89c2\u70b9\u4e2d\u201c\u80a9\u5e76\u80a9\u201d\u7684\u56fe\u50cf\uff08\u5373\u7c7b\u4f3c\u4e8e\u56fe\u4e2d\u7684Pipek-Mezey LMOs\uff09\uff0c\u6b64\u5904\u66f4\u63a5\u8fd1\u4e8eBoys LMOs\u7684\u53cc\u952e\u56fe\u50cf\u3002Pipek-Mezey LMOs\u5448\u73b0\u7684C-C\u53cc\u952e\u7684\u7ed3\u679c\u66f4\u7b26\u5408\u5316\u5b66\u76f4\u89c9\uff0cBoys LMOs\u5219\u5c06\u6b64\u5904\u7406\u6210\u4e86\u4e24\u4e2a\u7b49\u4ef7\u7684\u9999\u8549\u952e\u3002\u8fd9\u4e24\u79cd\u53cc\u952e\u7684\u63cf\u8ff0\u5f62\u5f0f\u6ca1\u6cd5\u8bf4\u8c01\u5bf9\u8c01\u9519\uff0c\u4ece\u7269\u7406\u89d2\u5ea6\u4e0a\u662f\u7b49\u4ef7\u7684\u63cf\u8ff0\uff0c\u53ea\u662f\u6070\u5de7\u5bf9\u4e8e\u672c\u4f8b\u6765\u8bf4\uff0cGVB\u6ce2\u51fd\u6570\u7684\u7ed3\u679c\u4e0eBoys\u7684\u7ed3\u679c\u66f4\u63a5\u8fd1\u3002\u660e\u767d\u8fd9\u4e00\u70b9\uff0c\u5bf9\u4e8e\u786e\u5b9a\u9700\u8981\u7eb3\u5165\u6d3b\u6027\u7a7a\u95f4\u7684\u8f68\u9053\u5e8f\u53f7\u5f88\u91cd\u8981\u3002\u4e8b\u5b9e\u4e0a\u5728\u53cc\u5360\u636e\u8f68\u9053\u4e2d\uff0c\u6bcf\u4e2a\u73af\u620a\u4e8c\u70ef\u8d1f\u79bb\u5b50\u80fd\u591f\u627e\u52308\u4e2a\u56fe\u50cf\u4f3c\u6b64\u7684\u8f68\u9053\uff0c\u663e\u7136\uff0c\u5176\u4e2d\u5360\u636e\u6570\u66f4\u63a5\u8fd1\u4e8e2\u76845\u4e2a\u8f68\u9053\u5bf9\u5e94\u4e8eC-C \u03c3\u8f68\u9053\uff0c\u5360\u636e\u6570\u504f\u79bb2\u8f83\u591a\u76843\u4e2a\u8f68\u9053\u4e3a\u03c0\u8f68\u9053\u3002<br>\u6211\u4eec\u9700\u8981\u5c06\u8fd915\u4e2a\u8f68\u9053\u901a\u8fc7\u8c03\u6362\u987a\u5e8f\u4f7f\u4e4b\u4f4d\u4e8e\u524d\u7ebf\u8f68\u9053\uff0c\u6b64\u65f6\u9700\u8981\u591a\u6b21\u8c03\u6362\u624d\u80fd\u5b8c\u6210\uff0c\u6b64\u5904\u63d0\u4f9b\u4e00\u4e2a\u4e00\u952e\u8c03\u6362\u8f68\u9053\u987a\u5e8f\u7684\u5c0f\u7a0b\u5e8fexmo.py\u3002\u8fd0\u884c\u4e4b\uff0c\u5f97\u5230\u91cd\u65b0\u6392\u5e8f\u540e\u7684\u6ce2\u51fd\u6570\u6587\u4ef6\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">python exmo.py ferrocene_uhf_uno_asrot2gvb29_s.fch \"22-24 35-37 46-48 49-51 60-62\"<\/code><\/pre>\n\n\n\n<p>\u7136\u540e\u4f7f\u7528\u6240\u5f97\u7684exchanged.fch\u4f5c\u4e3a\u521d\u731c\uff0c\u4eff\u71672.1\u548c2.2\u4e2d\u505a\u6cd5\u4f7f\u7528Gaussian\u5904\u7406\u6587\u4ef6\u683c\u5f0f\u95ee\u9898\uff0c\u7136\u540e\u8fdb\u884cCASSCF\u8ba1\u7b97\u3002\u5148\u4ea7\u751f\u542b\u6709\u5206\u5b50\u7ed3\u6784\u3001\u57fa\u7ec4\u7b49\u57fa\u672c\u4fe1\u606f\u7684PySCF\u8f93\u5165\u6587\u4ef6\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">bas_fch2py exchanged.fch<\/code><\/pre>\n\n\n\n<p>\u8fd9\u5c06\u4f1a\u5f97\u5230\u4e00\u4e2a\u65b0\u7684\u540d\u4e3aexchanged.py\u7684PySCF\u8f93\u5165\u6587\u4ef6\u3002\u4eff\u71672.1\u548c2.2\u4e2d\u505aCASSCF\u8ba1\u7b97\u7684\u8f93\u5165\u6587\u4ef6\uff0c\u8865\u5145\u5f00\u5934import\u4ee5\u53caCASSCF\u8ba1\u7b97\u7684\u90e8\u5206\u4ee3\u7801\u5373\u53ef\u63d0\u4ea4\u4efb\u52a1\u3002\u6b64\u5916\uff0c\u672c\u4f8b\u6240\u9009\u7684(15o,18e)\u6d3b\u6027\u7a7a\u95f4\u867d\u7136\u8db3\u591f\u5b8c\u5584\uff0c\u4f46\u8ba1\u7b97\u91cf\u8f83\u5927\uff0c\u8fd9\u6837\u5c3a\u5bf8\u7684\u6d3b\u6027\u7a7a\u95f4\u4e00\u822c\u53ef\u4ee5\u505aDMRG-SCF\u4ee5\u8282\u7701\u8ba1\u7b97\u91cf\u3002<\/p>\n\n\n\n<p><strong>3. \u4e3a\u53cd\u5e94\u8fc7\u7a0b\u62df\u5b9a\u7edf\u4e00\u7684\u6d3b\u6027\u7a7a\u95f4\uff1a\u57fa\u4e8eGVB\u6ce2\u51fd\u6570<\/strong><\/p>\n\n\n\n<p>\u7531\u4e8e\u4e3a\u4e86\u6bd4\u8f83\u4e0d\u540c\u4e2d\u95f4\u4f53\/\u8fc7\u6e21\u6001\u7684\u80fd\u91cf\uff0c\u4f7f\u7528\u591a\u53c2\u8003\u65b9\u6cd5\u8ba1\u7b97\u66f4\u7cbe\u786e\u7684\u7535\u5b50\u80fd\u91cf\u65f6\uff0c\u5fc5\u987b\u4fdd\u8bc1\u6d3b\u6027\u7a7a\u95f4\u7684\u5c3a\u5bf8\u4e00\u81f4\uff0c\u4e14\u6d3b\u6027\u7a7a\u95f4\u5185\u6240\u5305\u542b\u7684\u8f68\u9053\u76f8\u8fd1\u3002\u6211\u4eec\u4ee5<a href=\"https:\/\/pubs.rsc.org\/en\/content\/articlelanding\/2020\/cp\/d0cp02834g\" target=\"_blank\" rel=\"noreferrer noopener\"><em>Phys. Chem. Chem. Phys.<\/em>, <strong>2020,<\/strong> <em>22<\/em>, 17677-17686<\/a>\u4e2d\u6240\u7814\u7a76\u7684Fe\u50ac\u5316\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u4e3a\u4f8b\uff0c\u8bb2\u89e3\u5982\u4f55\u4e3a\u4e0d\u540c\u7ed3\u6784\u9009\u62e9\u5c3d\u91cf\u7edf\u4e00\u7684\u6d3b\u6027\u7a7a\u95f4\u3002\u9996\u5148\u4f7f\u7528SI\u4e2d\u6240\u63d0\u4f9b\u7684\u7ed3\u6784\uff0c\u5728PBE0-D3(BJ)\/def2-SVP\u7ea7\u522b\u4e0b\u91cd\u65b0\u4f18\u5316\uff0c\u5728\u4f18\u5316\u5b8c\u6bd5\u7684\u7ed3\u6784\u57fa\u7840\u4e0a\uff0c\u4f7f\u7528MOKIT\u505a\u81ea\u52a8GVB\/def2-TZVP\u8ba1\u7b97\u3002\u8be5\u53cd\u5e94\u5982\u4e0b\uff1a<\/p>\n\n\n\n<p><strong>3.1 RC (S = 3\/2)<br><\/strong>\u6839\u636eGVB\u7ed3\u679c\uff0c\u5360\u636e\u6570\u4ecb\u4e8e0.02-1.98\u8303\u56f4\u7684\u8f68\u9053\u5305\u542b\u4ee5\u4e0b13\u4e2a\u3002\u53ef\u4ee5\u53d1\u73b0\uff0c102-105\u548c111-114\u662f4\u4e2a\u82ef\u57fa\u9634\u79bb\u5b50\u76844\u5bf9\u03c0\/\u03c0*\u8f68\u9053\uff0c106\u548c110\u662fFe-C\u914d\u4f4d\u952e\u7684\u03c3\/\u03c3*\u8f68\u9053\uff0c\u4e14\u5177\u6709\u5f62\u4f3cd\u8f68\u9053\u7684\u6210\u5206\uff0c107-109\u662f3\u4e2a\u5355\u5360\u636e\u7684d\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"445\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-11-1024x445.png\" alt=\"\" class=\"wp-image-1911\" style=\"width:840px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-11-1024x445.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-11-300x130.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-11-768x334.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-11-583x253.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-11.png 1224w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u6211\u4eec\u9996\u5148\u5c06\u6211\u4eec\u7684\u7ed3\u679c\u4e0e\u539f\u6587\u732e\u4e2d\u7684(21o,21e)\u6d3b\u6027\u7a7a\u95f4\u5bf9\u6bd4\u3002\u539f\u6587\u9996\u5148\u57fa\u4e8eUKS\u6ce2\u51fd\u6570\u5f97\u5230\u4e86UNO\u6ce2\u51fd\u6570\uff0c\u7136\u540e\u6839\u636eNOON (natural orbital occupation number)\u4ecb\u4e8e0.03-1.97\u7684\u9608\u503c\u9009\u62e9\u6d3b\u6027\u7a7a\u95f4\uff0c\u5171\u5305\u542b\u4e864\u4e2a\u82ef\u57fa\u9634\u79bb\u5b50\u7684\u51718\u5bf9\u03c0\/\u03c0*\u8f68\u9053\u548c5\u4e2a3d\u8f68\u9053\uff0c\u5e76\u5c06\u6b64\u6d3b\u6027\u7a7a\u95f4\u5c3a\u5bf8\u5e94\u7528\u4e8e\u5176\u4ed6\u4e2d\u95f4\u4f53\u548c\u8fc7\u6e21\u6001\uff0c\u4ee5\u6536\u655b\u7684CASSCF\u6ce2\u51fd\u6570\u505aNEVPT2\u8ba1\u7b97\u4ee5\u83b7\u5f97\u51c6\u786e\u7684\u7535\u5b50\u80fd\u91cf\u3002\u6211\u4eec\u4e0d\u8ba8\u8bba\u8be5\u5de5\u4f5c\u6d41\u7a0b\u662f\u5426\u5408\u9002\uff0c\u4ec5\u601d\u8003\u8fd9\u90e8\u5206\u8f68\u9053\u662f\u5426\u9002\u7528\u4e8e\u6574\u4e2a\u53cd\u5e94\u3002<br>\u8fd9\u91cc\u8ba1\u7b97\u7684\u5b9e\u9645\u4e0a\u662f\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u4e2d\u7684\u8fd8\u539f\u6d88\u9664\u6b65\u9aa4\uff0c\u56e0\u6b64\u5076\u8054\u4e24\u4e2a\u82b3\u73af\u7684\u5b64\u5bf9\u7535\u5b50\uff0c\u5176\u4e2d\u4e00\u5bf9\u5f62\u6210Ar-Ar\u952e\uff0c\u53e6\u4e00\u5bf9\u8f6c\u79fb\u7ed9Fe(III)\u5f62\u6210Fe(I)\u3002\u6545\u6d3b\u6027\u7a7a\u95f4\u5fc5\u987b\u5305\u542b\u8fd9\u4e00\u90e8\u5206\u8f68\u9053\u624d\u80fd\u591f\u51c6\u786e\u63cf\u8ff0\u53cd\u5e94\u8fc7\u7a0b\uff0c\u5e76\u7ed9\u51fa\u53ef\u6bd4\u8f83\u7684\u7535\u5b50\u80fd\u91cf\u3002\u4f46\u5728\u539f\u6587\u7684(21o,21e)\u6d3b\u6027\u7a7a\u95f4\u4e2d\uff0c\u8fd9\u4e00\u90e8\u5206\u8f68\u9053\u5374\u5e76\u672a\u5b8c\u5168\u8003\u8651\u5230\u3002\u540c\u65f6\u6211\u4eec\u4f1a\u6ce8\u610f\u5230\uff0c\u5728\u539f\u6587\u4f7f\u7528UKS\u5f97\u5230\u7684UNO\u6ce2\u51fd\u6570\u4e2d\uff0cFe-C\u914d\u4f4d\u952e\u6bd4\u8f83\u5f7b\u5e95\u5730\u88ab\u5212\u5206\u6210d\u8f68\u9053\u548cLP\u8f68\u9053\uff0c\u56e0\u6b64LP\u8f68\u9053\uff08\u7684\u6210\u5206\uff09\u5e76\u672a\u51fa\u73b0\u5728\u6d3b\u6027\u7a7a\u95f4\u4e2d\u3002<br>GVB\u6ce2\u51fd\u6570\u7684\u7ed3\u679c\u5982\u4f55\u5462\uff1f\u5982\u56fe\u6240\u793a\uff0c106\u548c110\u8f68\u9053\u662f\u6211\u4eec\u9700\u8981\u8003\u8651\u7684Fe-C\u952e\u8f68\u9053\uff0c\u4f46\u4e0d\u662f\u5b9e\u9645\u53d1\u751f\u53cd\u5e94\u7684\u4e00\u7ec4\uff0c\u6211\u4eec\u5e0c\u671b\u8003\u5bdf\u7684\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u6d89\u53ca\u5e26\u6709\u6c28\u57fa\u53d6\u4ee3\u7684\u82ef\u57fa\u9634\u79bb\u5b50\u53ca\u5176\u90bb\u4f4d\u7684\u82ef\u57fa\u9634\u79bb\u5b50\u3002GVB\u8f68\u9053\u5360\u636e\u65700.02-1.98\u7684\u8303\u56f4\u5185\u5e76\u672a\u5305\u62ec\u6211\u4eec\u5e0c\u671b\u5f97\u5230\u7684\u4e24\u5bf9\u8f68\u9053\uff0c\u53ef\u80fd\u539f\u56e0\u662f\u5904\u4e8e\u6c28\u57fa\u82ef\u57fa\u9634\u79bb\u5b50\u5bf9\u4f4d\u7684\u82ef\u57fa\u9634\u79bb\u5b50\u53d7\u5176\u5f71\u54cd\uff0c\u8f68\u9053\u5360\u636e\u6570\u521a\u597d\u4f4d\u4e8e\u8303\u56f4\u4e4b\u5185\u3002\u4f46\u8fd9\u5e76\u4e0d\u91cd\u8981\uff0c\u6211\u4eec\u53ef\u4ee5\u5f88\u5bb9\u6613\u8fa8\u8ba4\u51fa46\u300147\u300158\u3001106\u3001110\u3001158\u3001169\u548c170\u662f4\u5bf9Fe-C\u6210\u53cd\u952e\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"352\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-17-1024x352.png\" alt=\"\" class=\"wp-image-1930\" style=\"width:840px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-17-1024x352.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-17-300x103.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-17-768x264.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-17-583x201.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-17.png 1116w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u73b0\u5728\u6211\u4eec\u81ea\u7136\u800c\u7136\u5c31\u4f1a\u4ea7\u751f\u4e00\u4e2a\u7591\u95ee\u3002\u89c2\u5bdf\u56fe\u4e2d\u7684\u8fd9\u4e9bFe-C\u952e\u8f68\u9053\uff0c\u4ed6\u4eec\u90fd\u8868\u73b0\u51fad\u8f68\u9053\u7684\u6210\u5206\u3002\u7406\u8bba\u4e0a\u6765\u8bf4\uff0c\u82e5d\u8f68\u9053\u4e0eLP\u8f68\u9053\u5f62\u6210\u914d\u4f4d\u952e\uff0c4\u5bf9Fe-C\u952e\u8f68\u9053\u5c31\u8981\u6d89\u53ca\u52304\u4e2ad\u8f68\u9053\uff0c\u52a0\u4e0a\u5355\u5360\u76843\u4e2ad\u8f68\u9053 (107-109)\uff0c\u603b\u6570\u8fbe\u5230\u4e867\u4e2a\uff0c\u8fd9\u662f\u8fdd\u53cd\u5e38\u7406\u7684\u3002\u5982\u4f55\u7406\u89e3\u8fd9\u4e00\u60c5\u51b5\u5462\uff1f\u914d\u4f53\u573a\u7406\u8bba\u6307\u51fa\uff0c\u5bf9\u4e8e\u5e73\u9762\u56db\u65b9\u5f62\u573a\uff0c\u7528\u4e8e\u6210\u952e\u7684d\u8f68\u9053\u53ea\u6709\u4e00\u4e2a\uff0c\u6b64\u5904\u5373\u4e3adsp<sup>2<\/sup>\u6742\u5316\uff0c\u540c\u65f6\u8fd8\u67091\u4e2a4p\u8f68\u9053\u672a\u53c2\u4e0e\u6742\u5316\u3002\u56e0\u6b64\uff0c\u5f53\u6211\u4eec\u8003\u8651\u4efb\u4f55\u4e00\u4e2aFe-C\u952e\u65f6\uff0c\u6211\u4eec\u5c31\u5fc5\u8981\u8981\u8003\u8651\u6240\u67094\u4e2aFe-C\u952e\uff0c\u8fd9\u4e5f\u5c31\u540c\u65f6\u8003\u8651\u4e86Fe\u539f\u5b509\u4e2a\u4ef7\u5c42\u8f68\u9053\u4e2d\u76847\u4e2a\u3002\u800cd<sub>z2<\/sub>\u548cp<sub>z<\/sub>\u5728\u8be5\u53cd\u5e94\u4e2d\u5e76\u672a\u6d89\u53ca\uff0c\u6545\u6392\u9664\u5728\u6d3b\u6027\u7a7a\u95f4\u4e4b\u5916\u3002\u8fd9\u4e5f\u544a\u8bc9\u6211\u4eec\uff0c\u5728\u9009\u62e9d\u533a\u91d1\u5c5e\u539f\u5b50\u7684\u6d3b\u6027\u7a7a\u95f4\u65f6\uff0c\u5e76\u4e0d\u603b\u662f\u9700\u8981\u5c06\u6240\u6709\u7684d\u8f68\u9053\u7eb3\u5165\u6d3b\u6027\u7a7a\u95f4\u8003\u5bdf\uff08\u867d\u7136\u5f88\u591a\u6587\u732e\u90fd\u8fd9\u4e48\u505a\uff09\uff0c\u8003\u8651\u8ba1\u7b97\u6210\u672c\u65f6\uff0c\u53ef\u4ee5\u6839\u636e\u5b9e\u9645\u60c5\u51b5\u5220\u51cf\u4e0d\u91cd\u8981\u7684\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"818\" height=\"404\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-16.png\" alt=\"\" class=\"wp-image-1923\" style=\"width:600px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-16.png 818w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-16-300x148.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-16-768x379.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-16-583x288.png 583w\" sizes=\"auto, (max-width: 818px) 100vw, 818px\" \/><\/figure>\n<\/div>\n\n\n<p>\u63a5\u4e0b\u6765\u6211\u4eec\u8ba8\u8bba\u914d\u4f53\u7684\u03c0\/\u03c0*\u8f68\u9053\u3002\u5728\u6b64\u4e4b\u524d\uff0c\u6211\u4eec\u4e0d\u59a8\u5bf9\u6bd4\u4e00\u4e0b\u57fa\u4e8eGVB\u8f68\u9053\u5360\u636e\u6570\u7ed9\u51fa\u7684\u82ef\u73af\u4e0e\u82ef\u57fa\u9634\u79bb\u5b50\u7684\u6d3b\u6027\u7a7a\u95f4\u3002\u76f8\u8f83\u4e8e\u82ef\u73af\u76846\u4e2a\u03c0\/\u03c0*\u8f68\u9053\uff0c\u82ef\u57fa\u9634\u79bb\u5b50GVB\u8f68\u9053\u5360\u636e\u6570\u4ecb\u4e8e0.02-1.98\u4e4b\u95f4\u7684\u4ec5\u6709\u56db\u4e2a\u8f68\u9053\uff0c\u5176\u4e0e\u82ef\u73af\u7684\u03c0\/\u03c0*\u8f68\u9053\u7684\u5bf9\u5e94\u5173\u7cfb\u5982\u56fe\u6240\u793a\u3002\u82ef\u57fa\u9634\u79bb\u5b50\u5177\u6709\u8f83\u5f3a\u591a\u53c2\u8003\u6027\u768420\/23\u8f68\u9053\uff0c\u6b63\u5bf9\u5e94\u4e8eRC (S = 3\/2) \u6240\u5f97GVB\u8f68\u9053\u7684102-105\u548c111-114\u3002\u76f8\u5e94\u5730\uff0c\u6211\u4eec\u4e5f\u53ef\u4ee5\u5728GVB\u8f68\u9053\u4e2d\u627e\u523021\/22\u6240\u5bf9\u5e94\u7684\u53e6\u59164\u5bf9\u03c0\/\u03c0*\u8f68\u9053\u3002\u7531\u4e8e\u82ef\u57fa\u9634\u79bb\u5b50\u4ec5\u4ee5LP\u8f68\u9053\u914d\u4f4d\uff0c\u03c0\/\u03c0*\u8f68\u9053\u4ec5\u4e8e\u91d1\u5c5e\u4e2d\u5fc3\u539f\u5b50\u6709\u8f83\u5f31\u7684d-\u03c0\u5171\u8f6d\uff0c\u56e0\u6b64\u4ecd\u7136\u4fdd\u7559\u4e86\u5b64\u7acb\u82ef\u57fa\u9634\u79bb\u5b50\u4e2d\u7684\u8f68\u9053\u56fe\u50cf\uff0c\u5bb9\u6613\u8fa8\u8ba4\u51fa84\u300198\u3001100\u3001101\u3001115\u3001116\u3001118\u548c132\u8f68\u9053\u662f\u6211\u4eec\u60f3\u627e\u51fa\u7684\u7b2c\u4e8c\u7ec4\u51718\u4e2a\u03c0\/\u03c0*\u8f68\u9053\u3002<\/p>\n\n\n\n<figure class=\"wp-block-image size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"247\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14-1024x247.png\" alt=\"\" class=\"wp-image-1935\" style=\"width:1159px;height:auto\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14-1024x247.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14-300x72.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14-768x185.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14-1536x370.png 1536w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14-583x141.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-14.png 2024w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n\n\n\n<p>\u6839\u636e\u4ee5\u4e0a\u8ba8\u8bba\uff0c\u6211\u4eec\u53ef\u4ee5\u4e3aRC (S = 3\/2)\u6784\u5efa\u4e09\u79cd\u4e0d\u540c\u5927\u5c0f\u7684\u6d3b\u6027\u7a7a\u95f4\uff1a<\/p>\n\n\n\n<figure class=\"wp-block-table is-style-stripes has-small-font-size\"><table class=\"has-fixed-layout\"><tbody><tr><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">Size of active space<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">Fe valence<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">Fe-phenyl \u03c3\/\u03c3*<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">phenyl \u03c0\/\u03c0* (1)<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">phenyl \u03c0\/\u03c0* (2)<\/mark><\/td><\/tr><tr><td>(11o,11e)<\/td><td>107-109<\/td><td>46, 47, 58, 106<br>110, 158, 169, 170<\/td><td>\u2014<\/td><td>\u2014<\/td><\/tr><tr><td>(19o,19e)<\/td><td>107-109<\/td><td>46, 47, 58, 106<br>110, 158, 169, 170<\/td><td>102-105<br>111-114<\/td><td>\u2014<\/td><\/tr><tr><td>(27o,27e)<\/td><td>107-109<\/td><td>46, 47, 58, 106<br>110, 158, 169, 170<\/td><td>102-105<br>111-114<\/td><td>84, 98, 100, 101<br>115, 116, 118, 132<\/td><\/tr><\/tbody><\/table><\/figure>\n\n\n\n<p><strong>3.2 TS-cross (S = 3\/2)<br><\/strong>\u5728\u8fc7\u6e21\u6001\u5904\uff0c\u8be5\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\u7684\u8f68\u9053\u8868\u793a\u5982\u4e0b\uff1a<br>2 (\u03c3 dsp<sup>2<\/sup>-LP) + 2 (\u03c3* dsp<sup>2<\/sup>-LP) \u27f6 (LP-LP \u03c3) + (LP-LP \u03c3*) + (LP-dsp<sup>2<\/sup>-LP 3c-2e) + (LP-dsp<sup>2<\/sup>-LP 3c-2e*)<br>\u6211\u4eec\u53ef\u4ee5\u627e\u5230\u5bf9\u5e94\u4e8e\u5373\u5c06\u5f62\u6210\u7684C-C\u952e\u7684\u03c3\/\u03c3*\u8f68\u9053\uff0c\u4ee5\u53ca\u4e00\u7ec4\u5f62\u5982C-Fe-C\u4e09\u4e2d\u5fc3\u4e24\u7535\u5b50\u952e\u7684\u8f68\u9053\uff0c\u4ee5\u4ee3\u66ff\u539f\u6709\u7684\u4e24\u7ec4Fe-C\u952e\u7684\u03c3\/\u03c3*\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"324\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-18-1024x324.png\" alt=\"\" class=\"wp-image-1940\" style=\"width:800px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-18-1024x324.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-18-300x95.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-18-768x243.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-18-583x185.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-18.png 1226w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u9664\u6b64\u4e4b\u5916\uff0c\u5176\u4ed6\u8f68\u9053\u5747\u4e0eRC (S = 3\/2)\u7c7b\u4f3c\uff0c\u76f8\u5e94\u7684\u4e09\u79cd\u4e0d\u540c\u5c3a\u5bf8\u7684\u6d3b\u6027\u7a7a\u95f4\u4e3a\uff1a<\/p>\n\n\n\n<figure class=\"wp-block-table is-style-stripes has-small-font-size\"><table class=\"has-fixed-layout\"><tbody><tr><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">Size of active space<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">Fe valence<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">Fe-phenyl \u03c3\/\u03c3*<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">phenyl \u03c0\/\u03c0* (1)<\/mark><\/td><td><mark style=\"background-color:rgba(0, 0, 0, 0)\" class=\"has-inline-color has-accent-2-color\">phenyl \u03c0\/\u03c0* (2)<\/mark><\/td><\/tr><tr><td>(11o,11e)<\/td><td>107-109<\/td><td>62, 63, 153, 154<br>106, 110 (C-Fe-C 3c-2e\/3c-2e*)<br>43, 173 (C-C \u03c3\/\u03c3*)<\/td><td>\u2014<\/td><td>\u2014<\/td><\/tr><tr><td>(19o,19e)<\/td><td>107-109<\/td><td>62, 63, 153, 154<br>106, 110 (C-Fe-C 3c-2e\/3c-2e*)<br>43, 173 (C-C \u03c3\/\u03c3*)<\/td><td>102-105<br>111-114<\/td><td>\u2014<\/td><\/tr><tr><td>(27o,27e)<\/td><td>107-109<\/td><td>62, 63, 153, 154<br>106, 110 (C-Fe-C 3c-2e\/3c-2e*)<br>43, 173 (C-C \u03c3\/\u03c3*)<\/td><td>102-105<br>111-114<\/td><td>77, 81, 99, 101<br>115, 117, 135, 139<\/td><\/tr><\/tbody><\/table><\/figure>\n\n\n\n<p><strong>3.3 MC-PDFT<\/strong><br>\u9009\u62e9\u4ee5\u4e0a\u6d3b\u6027\u7a7a\u95f4\u540e\uff0c\u6211\u4eec\u5df2\u7ecf\u53ef\u4ee5\u5bf9RC\u548cTS\u8fdb\u884c(DMRG-)CASSCF\u8ba1\u7b97\uff0c\u5e76\u57fa\u4e8eCASSCF\u6ce2\u51fd\u6570\u8fdb\u884cMC-PDFT\u8ba1\u7b97\uff0c\u4ece\u800c\u5f97\u5230\u53cd\u5e94\u7684\u80fd\u5792\u3002(DMRG-)CASSCF\u8ba1\u7b97\u7684\u6d41\u7a0b\u53ef\u4ee5\u4eff\u7167\u524d\u6587\u5b8c\u6210\uff0c\u8ba1\u7b97\u7ed3\u675f\u540e\uff0c\u5f97\u5230\u81ea\u7136\u8f68\u9053*NO.fch\uff0c\u89c2\u5bdf\u6536\u655b\u540e\u7684\u8f68\u9053\u662f\u5426\u5408\u7406\u3002\u7136\u540e\u8bfb\u53d6\u81ea\u7136\u8f68\u9053\u505aMC-PDFT\u8ba1\u7b97\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">bas_fch2py *NO.fch<\/code><\/pre>\n\n\n\n<p>\u5728\u5f97\u5230\u7684*NO.py\u7ed3\u5c3e\u6dfb\u52a0MC-PDFT\u8ba1\u7b97\u7684\u76f8\u5173\u4ee3\u7801\uff08\u53ef\u901a\u8fc7automr\u505a\u4e00\u4e2a\u5c0f\u4efb\u52a1\u5f97\u5230\u6a21\u677f\uff09\uff1a<\/p>\n\n\n\n<pre class=\"wp-block-code has-small-font-size\"><code class=\"\">mc = mcpdft.CASCI(mf,'tPBE',19,(11,8)) # \u53ef\u9009\u7684\u6cdb\u51fd\u5f62\u5f0f\u53c2\u8003PySCF\u8bf4\u660e\u6587\u6863\u3002<br>mc.grids.atom_grid = (99,590)<br>mc.max_memory = 48000 # MB<br>mc.fcisolver = dmrgscf.DMRGCI(mol, maxM=1000)<br>mc.fcisolver.threads = nproc<br>mc.fcisolver.memory = 48 # GB<br>mc.kernel()<\/code><\/pre>\n\n\n\n<p>\u5bf9\u4e8e\u672c\u4f8b\uff0c\u4f7f\u7528(11o,11e)\u6d3b\u6027\u7a7a\u95f4\u5f97\u5230\u7684\u7535\u5b50\u80fd\u5792\u4ec5\u7ea63 kcal\u00b7mol<sup>-1<\/sup>\uff0c\u8fd9\u662f\u660e\u663e\u4e0d\u5408\u7406\u7684\uff0c\u8bf4\u660e\u8003\u8651\u82ef\u73af\u914d\u4f53\u7684\u03c0\/\u03c0*\u8f68\u9053\u662f\u5fc5\u8981\u7684\u3002\u4f7f\u7528(19o,19e)\u548c(27o,27e)\u6d3b\u6027\u7a7a\u95f4\u5f97\u5230\u7684\u7535\u5b50\u80fd\u5792\u5747\u572816 kcal\u00b7mol<sup>-1<\/sup>\u5de6\u53f3\uff0c\u8fd9\u4e0e\u539f\u6587\u7684\u7ed3\u679c\u63a5\u8fd1\uff0c\u4e5f\u4e0e\u5b9e\u9a8c\u7ed3\u679c\u6bd4\u8f83\u7b26\u5408\u3002<\/p>\n\n\n\n<p><strong>3.4 P-cross\/near (S = 1\/2)<\/strong><br>P-cross\/near (S = 1\/2)\u7684\u7ed3\u6784\u4e2d\uff0c\u5076\u8054\u4ea7\u7269\u7684\u4e00\u4e2a\u82ef\u73af\u4ee5\u03c0\u914d\u4f53\u7684\u5f62\u5f0f\u4e0eFe(I)\u914d\u4f4d\uff0c\u56e0\u6b64\u8be5\u82ef\u73af\u7684\u03c0\u8f68\u9053\u9009\u62e9\u5c06\u4f1a\u4e0eRC\u548cTS\u4e0d\u540c\u3002\u6211\u4eec\u9996\u5148\u786e\u5b9a\u5176\u4ed6\u4e09\u4e2a\u82ef\u73af\/\u82ef\u57fa\u9634\u79bb\u5b50\u7684\u03c0\u8f68\u9053\u3002\u5728\u5360\u636e\u6570\u4ecb\u4e8e0.02-1.98\u8303\u56f4\u7684GVB\u8f68\u9053\u4e2d\uff0c\u53ef\u4ee5\u627e\u5230104-106\u548c110-112\u51713\u7ec46\u4e2a\u03c0\/\u03c0*\u8f68\u9053\u3002\u8003\u8651\u5230104\u3001105\u3001111\u548c112\u5c5e\u4e8e\u540c\u4e00\u4e2a\u82ef\u73af\uff0c\u56e0\u6b64\u5c06105\/111\u8fd9\u4e00\u5bf9\u03c0\/\u03c0*\u8f68\u9053\u7eb3\u5165(19o,19e)\u6d3b\u6027\u7a7a\u95f4\uff0c104\/112\u5219\u7eb3\u5165(27o,27e)\u6d3b\u6027\u7a7a\u95f4\u3002\u9664\u6b64\u4e4b\u5916106\/110\u4e5f\u5c06\u5176\u7eb3\u5165(19o,19e)\u6d3b\u6027\u7a7a\u95f4\u8003\u8651\u3002\u6269\u5927\u8f68\u9053\u641c\u7d22\u7684\u8303\u56f4\uff0c\u8fd8\u53ef\u4ee5\u627e\u523090\u3001102\u3001103\u3001113\u3001114\u548c126\uff0c\u603b\u8ba112\u4e2a\u03c0\/\u03c0*\u8f68\u9053\uff0c\u8fd9\u5c31\u5305\u542b\u4e86\u8fd9\u4e09\u4e2a\u82ef\u73af\/\u82ef\u57fa\u9634\u79bb\u5b50\u9700\u8981\u7eb3\u5165\u6d3b\u6027\u7a7a\u95f4\u7684\u5168\u90e8\u03c0\/\u03c0*\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"334\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-19-1024x334.png\" alt=\"\" class=\"wp-image-1943\" style=\"width:800px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-19-1024x334.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-19-300x98.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-19-768x250.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-19-583x190.png 583w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-19.png 1050w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u63a5\u4e0b\u6765\u6211\u4eec\u786e\u5b9a\u53e6\u4e00\u4e2a\u82ef\u73af\u7684\u03c0\/\u03c0*\u8f68\u9053\u3002\u4e0e\u4e8c\u8302\u94c1\u7684GVB\u7ed3\u679c\u7c7b\u4f3c\uff0c\u90e8\u5206\u8f68\u9053\u4ee5Boys LMO\u7684\u5f62\u5f0f\u51fa\u73b0\uff0c\u6b64\u65f6\u6211\u4eec\u9996\u5148\u9700\u8981\u6392\u9664\u03c3\/\u03c3*\u8f68\u9053\u7684\u5e72\u6270\u3002\u82ef\u73af\u5171\u67096\u7ec4\u03c3\/\u03c3*\u8f68\u9053\uff0c\u6211\u4eec\u53ef\u4ee5\u76f4\u63a5\u627e\u52304\u7ec4\uff0c\u5206\u522b\u662f59\u300161-63\u3001153-155\u548c157\uff0c\u4ed6\u4eec\u5177\u6709\u5f88\u660e\u663e\u7684\u03c3\u5bf9\u79f0\u6027\u3002\u9664\u6b64\u4e4b\u5916\uff0c\u8fd8\u670948\u300164\u300167\u300174\u300178\u3001138\u3001142\u3001149\u548c152\u51719\u4e2a\u8f68\u9053\u5177\u6709Boys LMO\u7684\u5f62\u5f0f\uff0c\u5176\u4e2d\u5c06\u4f1a\u67092\u7ec4\u03c3\/\u03c3*\u8f68\u9053\u3002\u89c2\u5bdf\u5df2\u77e5\u76844\u7ec4\u03c3\/\u03c3*\u8f68\u9053\uff0c\u6211\u4eec\u4e0d\u96be\u53d1\u73b0\uff0c\u6709\u4e24\u6839\u5904\u4e8e\u5bf9\u4f4d\u7684C-C\u952e\u672a\u627e\u5230\u5bf9\u5e94\u7684\u03c3\/\u03c3*\u8f68\u9053\uff0c\u6545\u5e94\u5728Boys LMO\u4e2d\u627e\u5230\u5206\u5e03\u5728\u8fd9\u4e24\u6839C-C\u952e\u4e0a\u7684\u8f68\u9053\u3002\u53c2\u8003\u4e8c\u8302\u94c1\u7684\u5904\u7406\u65b9\u6cd5\uff0c64\/152\u548c67\/149\u662f\u4e24\u7ec4\u03c3\/\u03c3*\u8f68\u9053\uff0c74\/142\u548c78\/138\u5219\u662f\u4e24\u7ec4\u03c0\/\u03c0*\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"615\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-20-1024x615.png\" alt=\"\" class=\"wp-image-1944\" style=\"width:840px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-20-1024x615.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-20-300x180.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-20-768x461.png 768w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-20-499x300.png 499w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-20.png 1112w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><\/figure>\n<\/div>\n\n\n<p>\u4f46\u6211\u4eec\u4f1a\u53d1\u73b0\uff0c48\u53f7\u8f68\u9053\u4e5f\u662f\u4e00\u4e2a\u03c0\u8f68\u9053\uff0c\u4f46\u5374\u5e76\u6ca1\u6709\u627e\u5230\u4e0e\u5176\u5bf9\u5e94\u7684\u03c0*\u8f68\u9053\u3002\u8003\u8651\u5230SOMO\u4e3a108\u53f7\u8f68\u9053\uff0c48\u53f7\u8f68\u9053\u7684\u53cd\u952e\u8f68\u9053\u7406\u8bba\u4e0a\u4e3a108*2-48=168\u53f7\u8f68\u9053\u3002\u4f46\u4e8b\u5b9e\u4e0a\u89c2\u5bdf168\u53f7\u8f68\u9053\u7684\u7b49\u503c\u9762\u540e\u4f1a\u53d1\u73b0\u4e8c\u8005\u5e76\u6ca1\u6709\u76f4\u63a5\u8054\u7cfb\uff0c\u4e0d\u5177\u6709\u5316\u5b66\u610f\u4e49\u4e0a\u7684\u6210\u53cd\u952e\u5bf9\u5e94\u7279\u5f81\uff0c\u56e0\u6b64\u8be5\u82ef\u73af\u786e\u5b9e\u7f3a\u5c11\u4e00\u4e2a\u03c0*\u8f68\u9053\u3002\u4f46\u89c2\u5bdf\u5360\u636e\u6570\u4ecb\u4e8e0.02-1.98\u4e4b\u95f4\u7684GVB\u8f68\u9053\u4e0d\u96be\u53d1\u73b0\uff0c107\u548c109\u53f7\u8f68\u9053\u4e3ad-\u03c0\u6210\u53cd\u952e\u8f68\u9053\uff0c\u4e14\u6211\u4eec\u53ef\u4ee5\u53d1\u73b0\u5b83\u4eec\u76f8\u4f4d\u7684\u5206\u5e03\u5f62\u4f3c\u201c\u9762\u5bf9\u9762\u201d\u6210\u952e\uff0c\u82e5\u4ee5\u901a\u8fc7Fe\u539f\u5b50\u4e14\u5e73\u884c\u4e8e\u82ef\u73af\u7684\u65b9\u5411\u4e3az\u65b9\u5411\uff0c\u8fd9\u7ec4\u8f68\u9053\u5b9e\u9645\u4e0a\u662f\u7531d<sub>xz<\/sub>\uff08\u6216d<sub>yz<\/sub>\uff09\u4e0e\u03c0*\u8f68\u9053\u76f8\u4e92\u4f5c\u7528\u5f62\u6210\u3002\u5728RC (S = 3\/2)\u4e2d\uff0cd<sub>xz<\/sub>\u548cd<sub>yz<\/sub>\u5747\u4e3a\u5355\u5360\u8f68\u9053\uff0c\u8fd8\u539f\u6d88\u9664\u540e\uff0c\u4e8c\u8005\u5747\u8fd1\u4f3c\u4e3a\u4e3a\u53cc\u5360\u8f68\u9053\uff0c\u4e0e\u03c0*\u8f68\u9053\u5f62\u6210\u53cd\u9988\u952e\uff0c\u5448\u4f4e\u81ea\u65cb\u6001\u3002\u56e0\u6b64\u6211\u4eec\u5c31\u627e\u5230\u4e86\u7f3a\u5931\u7684\u03c0*\u8f68\u9053\u3002<\/p>\n\n\n<div class=\"wp-block-image\">\n<figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"572\" src=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-22-1024x572.png\" alt=\"\" class=\"wp-image-1948\" style=\"width:600px\" srcset=\"https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-22-1024x572.png 1024w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-22-300x168.png 300w, https:\/\/www.homechemer.com\/wp-content\/uploads\/2024\/08\/image-22-768x429.png 768w, 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