{"id":153,"date":"2022-06-17T01:59:29","date_gmt":"2022-06-16T17:59:29","guid":{"rendered":"https:\/\/www.homechemer.com\/?p=153"},"modified":"2022-06-17T02:38:38","modified_gmt":"2022-06-16T18:38:38","slug":"spin-flip-tddft-in-q-chem-ver-5-4","status":"publish","type":"post","link":"https:\/\/www.homechemer.com\/computchem\/3","title":{"rendered":"\u5b89\u88c5\u53ca\u4f7f\u7528Q-Chem\u7a0b\u5e8f\u505aSpin-Flip TDDFT\u8ba1\u7b97\u5bfb\u627eS0-S1\u6781\u5c0f\u80fd\u91cf\u4ea4\u53c9\u70b9"},"content":{"rendered":"\n

\u5b89\u88c5\u53ca\u4f7f\u7528Q-Chem\u7a0b\u5e8f\u505aSpin-Flip TDDFT\u8ba1\u7b97\u5bfb\u627eS0<\/sub>-S1<\/sub>\u6781\u5c0f\u80fd\u91cf\u4ea4\u53c9\u70b9<\/strong>
Installing and Searching for S0<\/sub>-S1<\/sub> MECP with Spin-Flip TDDFT Method in Q-Chem<\/strong><\/p>\n\n\n\n

Jiawei Xu
Released: 2022-06-17 \/ Updated: 2022-06-17<\/p>\n\n\n\n

0. \u524d\u8a00<\/strong><\/p>\n\n\n\n

\u5bfb\u627e\u52bf\u80fd\u9762\u4e4b\u95f4\u7684\u6781\u5c0f\u80fd\u91cf\u4ea4\u53c9\u70b9(Minimum Energy Crossing Point, MECP)\u662f\u6fc0\u53d1\u6001\u7814\u7a76\u4e2d\u7ecf\u5e38\u9047\u5230\u7684\u95ee\u9898\u3002\u4f7f\u7528CASSCF\u65b9\u6cd5\u5bfb\u627eMECP\u662f\u6bd4\u8f83\u7406\u60f3\u7684\uff0c\u4f46CASSCF\u8ba1\u7b97\u91cf\u8f83\u5927\uff0c\u4e14\u6d89\u53ca\u6d3b\u6027\u7a7a\u95f4\u9009\u62e9\u7b49\u95ee\u9898\uff0c\u4f7f\u7528\u8d77\u6765\u4e0d\u662f\u5f88\u65b9\u4fbf\u3002\u76ee\u524d\u6d41\u884c\u7684TD-DFT\u65b9\u6cd5\u517c\u987e\u7cbe\u5ea6\u4e0e\u901f\u5ea6\uff0c\u4e0d\u5c11\u7a0b\u5e8f\u4e5f\u652f\u6301\u5728TD-DFT\u7ea7\u522b\u4e0b\u5bfb\u627eMECP\u70b9\uff0c\u4f8b\u5982GAMESS\u3001ORCA\u3001Q-Chem\u7b49\uff0cGaussian\u4e5f\u53ef\u4ee5\u901a\u8fc7Harvey\u7684MECP\u5916\u7f6e\u7a0b\u5e8f\u5b9e\u73b0\u3002GAMESS\u3001ORCA\u7b49\u7a0b\u5e8f\u624b\u518c\u7ed9\u51fa\u7684\u662f\u5bfb\u627eS0<\/sub>-S1<\/sub> MECP\u7684\u4f8b\u5b50\uff0c\u4f46\u5b9e\u9645\u4e0aTD-DFT\u5728\u63cf\u8ff0\u53c2\u8003\u6001(S0<\/sub>)\u4e0e\u6fc0\u53d1\u6001\u4e4b\u95f4MECP\u65f6\u5b58\u5728\u95ee\u9898\uff0c\u8fd9\u70b9\u5df2\u7ecf\u5728ORCA 5.0.2\u7248\u672c\u624b\u518c\u76848.3.12\u8282\u4e2d\u6307\u51fa\uff0c\u4e0d\u5c11\u6587\u732e\u4e5f\u63d0\u53ca\u4e86\u8fd9\u4e00\u89c2\u70b9\uff0c\u7a76\u5176\u539f\u56e0\u662fTD-DFT\u65b9\u6cd5\u4e0bS0<\/sub>-S1<\/sub> MECP\u7684\u53c2\u8003\u6001\u6ce2\u51fd\u6570\u4e3a\u5355\u884c\u5217\u5f0f\u6ce2\u51fd\u6570\uff0c\u4f46\u5728MECP\u9644\u8fd1\u5176\u591a\u53c2\u8003\u6027\u4e0d\u80fd\u5ffd\u7565\uff0c\u6545\u5b58\u5728\u7f3a\u9677\u3002\u5728\u8fd9\u4e00\u95ee\u9898\u4e0a\uff0cSpin-Flip TDDFT\u65b9\u6cd5\u80fd\u591f\u8f83\u597d\u5730\u5f25\u8865\u8fd9\u4e00\u7f3a\u9677\uff0c\u5c24\u5176\u662f\u5bf9\u5177\u6709\u53cc\u81ea\u7531\u57fa\u7279\u5f81\u7684\u4f53\u7cfb\u8868\u73b0\u6781\u4f73\uff0c\u7ed3\u679c\u4e0eCASPT2\u63a5\u8fd1\uff0c\u4f46\u8ba1\u7b97\u91cf\u4e0eTD-DFT\u76f8\u4eff\u4f5b\uff0c\u53ef\u4ee5\u5904\u7406\u8f83\u5927\u7684\u4f53\u7cfb\u3002\u672c\u6587\u901a\u8fc7\u51e0\u4e2a\u8ba1\u7b97\u5b9e\u4f8b\u7b80\u8981\u4ecb\u7ecd\u5728Q-Chem\u7a0b\u5e8f\u4e2d\u5229\u7528SF-TDDFT\u65b9\u6cd5\u5bfb\u627eMECP\u7684\u505a\u6cd5\u3002<\/p>\n\n\n\n

1. SF-TDDFT\u65b9\u6cd5\u7684\u539f\u7406<\/strong><\/p>\n\n\n\n

SF-TDDFT\u65b9\u6cd5\u901a\u8fc7\u7ffb\u8f6c\u53c2\u8003\u6001\u6ce2\u51fd\u6570\u4e2d\u7684\u4e00\u4e2a\u7535\u5b50\u81ea\u65cb\u7ed9\u51fa\u5355\u6fc0\u53d1\u7ec4\u6001\uff0c\u6fc0\u53d1\u6001\u6ce2\u51fd\u6570\u7531\u8fd9\u4e9b\u5355\u6fc0\u53d1\u7ec4\u6001\u7ebf\u6027\u7ec4\u5408\u800c\u6210\uff0c\u56e0\u6b64\u8ba1\u7b97\u91cf\u4e0eTD-DFT\u76f8\u4eff\u4f5b\u3002\u539f\u7406\u4e0a\u4e5f\u53ef\u4ee5\u7ffb\u8f6c\u591a\u4e2a\u7535\u5b50\u81ea\u65cb\u7ed9\u51fa\u591a\u6fc0\u53d1\u7ec4\u6001\uff0c\u4f46\u8fd9\u4e0d\u662fSF-TDDFT\u7684\u8303\u7574\uff0c\u6b64\u5904\u4e0d\u505a\u8ba8\u8bba\u3002\u5e38\u89c1\u7684\u505a\u6cd5\u662f\u901a\u8fc7\u7ffb\u8f6c\u4e09\u91cd\u6001\u53c2\u8003\u6001\u7684\u4e00\u4e2a\\alpha<\/span>\u7535\u5b50\u81ea\u65cb\u7ed9\u51fa\u5355\u91cd\u6001\uff0c\u8fd9\u65f6\u4e5f\u79f0\u4e3aFlip-Down TDDFT\u3002\u5bf9\u4e8e\u8fd9\u79cd\u60c5\u51b5\uff0c\u539f\u5148\u771f\u6b63\u7684\u57fa\u6001S0<\/sub>\u53ef\u80fd\u4f1a\u6210\u4e3aSF-TDDFT\u8ba1\u7b97\u4e2d\u7684S1<\/sub>\u6001\uff0c\u4e14\u7531\u591a\u4e2a\u884c\u5217\u6570\u7ebf\u6027\u7ec4\u5408\u63cf\u8ff0\uff0c\u5728\u4e00\u5b9a\u7a0b\u5ea6\u4e0a\u89e3\u51b3\u4e86\u666e\u901aTD-DFT\u8ba1\u7b97MECP\u65f6\u7684\u95ee\u9898\u3002<\/p>\n\n\n\n

2. Q-Chem\u7a0b\u5e8f\u7684\u5b89\u88c5<\/strong><\/p>\n\n\n\n

Q-Chem\u7a0b\u5e8f\u662f\u6536\u8d39\u7a0b\u5e8f\uff0c\u53ef\u4ee5\u5728\u5b98\u7f51\u4e0a\u83b7\u53d6\u8bd5\u7528\u7248\u672c(https:\/\/q-chem.com\/try\/<\/a>)\uff0c\u8bd5\u7528\u671f\u4e3a\u4e24\u4e2a\u6708\u3002\u8fdb\u5165\u8fd9\u4e00\u94fe\u63a5\u540e\u6309\u8981\u6c42\u586b\u5199\u76f8\u5173\u4fe1\u606f\uff0c\u4f1a\u6536\u5230Q-Chem\u516c\u53f8\u7684\u90ae\u4ef6\uff0c\u5176\u4e2d\u6709\u4e0e\u90ae\u7bb1\u7ed1\u5b9a\u7684\u8bd5\u7528\u53f7\u3002\u7136\u540e\u5728\u5b98\u65b9\u94fe\u63a5\u4e2d\u4e0b\u8f7d\u6240\u9700\u5e73\u53f0\u548c\u7248\u672c\u7684Q-Chem\u7a0b\u5e8f(https:\/\/q-chem.com\/install\/<\/a>)\uff0c\u6309\u7167\u6559\u7a0b\u5b89\u88c5\u3002\u5b89\u88c5\u8fc7\u7a0b\u4e2d\u4f1a\u63d0\u793a\u8f93\u5165\u7533\u8bf7\u8bd5\u7528\u7248\u672c\u7684\u90ae\u7bb1\u548c\u8bd5\u7528\u53f7\uff0c\u8054\u7f51\u60c5\u51b5\u4e0b\u7a0b\u5e8f\u4f1a\u81ea\u52a8\u67e5\u8be2\u662f\u5426\u6b63\u786e\uff0c\u6b63\u786e\u5219\u901a\u8fc7\u5b89\u88c5\u3002\u5bf9\u4e8e\u7f51\u7edc\u5f02\u5e38\u5bfc\u81f4\u7684\u4e0d\u80fd\u6b63\u5e38\u901a\u8fc7\uff0c\u4e00\u822c\u53ef\u4ee5\u4f7f\u7528\u79d1\u5b66\u4e0a\u7f51\u65b9\u6cd5\uff0c\u6216\u8005\u5c06license.data\u6587\u4ef6\u53d1\u90ae\u4ef6\u7ed9Q-Chem\u5ba2\u670d\uff0c\u5ba2\u670d\u4f1a\u53e6\u5916\u53d1\u9001\u4e0e\u673a\u5668\u7ed1\u5b9a\u7684license\uff0c\u53ef\u7528\u4e8e\u8fdb\u884c\u79bb\u7ebf\u5b89\u88c5\u3002\u5b89\u88c5\u5b8c\u6210\u540e\u5728\u8bd5\u7528\u671f\u5185\u53ef\u4ee5\u6b63\u5e38\u8fd0\u884c\u3002<\/p>\n\n\n\n

3. \u5b9e\u4f8b<\/strong><\/p>\n\n\n\n

3.1 \u4e59\u70ef<\/strong><\/p>\n\n\n\n

\u4e59\u70ef\u53cc\u952e\u7684\\pi<\/span>\u8f68\u9053\u6784\u62102e-2o\u6d3b\u6027\u7a7a\u95f4\uff0c\u5176S1<\/sub>\u6001\u53ef\u4ee5\u8fd1\u4f3c\u63cf\u8ff0\u4e3a\\pi^1\\pi^{*1}<\/span>\u3002\u4e59\u70ef\u53cc\u952e\u65cb\u8f6c\u7684\u8fc7\u7a0b\u4e2d\\pi<\/span>\u952e\u65ad\u88c2\uff0c\u4f53\u7cfb\u5177\u6709\u660e\u663e\u7684\u53cc\u81ea\u7531\u57fa\u7279\u5f81\uff0c\u5728\u4e24\u4e2a\u4e9a\u7532\u57fa\u5782\u76f4\u7684D2d<\/sub>\u7fa4\u7ed3\u6784\u4e0b\uff08\u4e0e\u4e19\u4e8c\u70ef\u7c7b\u4f3c\uff09\uff0cS0<\/sub>-S1<\/sub>\u4e24\u6001\u5b8c\u5168\u7b80\u5e76\u3002\u5728\u6574\u4e2a\u5706\u9525\u4ea4\u53c9(conical intersection, CI)\u7a7a\u95f4\u91cc\uff0cS0<\/sub>-S1<\/sub>\u4e24\u6001\u8fd1\u7b80\u5e76\u3002\u4e59\u70ef\u662f\u6700\u65e9\u4f7f\u7528SF-TDDFT\u8003\u5bdf\u7684\u4f53\u7cfb\uff0c\u5728J. Phys. Chem. A<\/em>, 2009<\/strong>, 113, 12749\u4e2d\u7814\u7a76\u4e86\u4e59\u70ef\u52bf\u80fd\u9762\u4e0a\u6bd4\u8f83\u6709\u5b9e\u9645\u610f\u4e49\u7684\u4e09\u4e2aS0<\/sub>-S1<\/sub> MECP\u70b9\uff0c\u5373PY-\u3001HM-\u548cET-MECP\u3002\u5728\u5149\u5f15\u53d1\u60c5\u51b5\u4e0b\uff0c\u4e59\u70ef\u53ef\u901a\u8fc7PY-MECP\u53d1\u751f\u53cc\u952e\u65cb\u8f6c\uff0c\u901a\u8fc7\u65e0\u8f90\u5c04\u65b9\u5f0f\u9000\u6fc0\u3002<\/p>\n\n\n

\n
\"\"<\/figure>\n<\/div>\n\n
\n
\"\"<\/figure>\n<\/div>\n\n\n

\u8f93\u5165\u6587\u4ef6\u53ef\u4ee5\u901a\u8fc7Q-Chem\u5b98\u65b9\u642d\u914d\u7684\u56fe\u5f62\u754c\u9762IQMol\u521b\u5efa\uff0c\u53ef\u4ee5\u5728\u5b98\u7f51\u4e0a\u514d\u8d39\u4e0b\u8f7d(https:\/\/q-chem.com\/try\/iqmol\/<\/a>)\uff0c\u4e5f\u53ef\u901a\u8fc7\u5176\u4ed6\u5e38\u89c1\u7684\u5efa\u6a21\u8f6f\u4ef6\u642d\u5efa\u5e76\u83b7\u5f97\u7ed3\u6784\u7684\u4e09\u7ef4\u5750\u6807\uff0c\u7136\u540e\u624b\u52a8\u5199\u4efb\u52a1\u63a7\u5236\u90e8\u5206\u3002\u7531\u4e8e\u4e00\u822c\u6700\u5e38\u7528\u7684\u91cf\u5316\u8ba1\u7b97\u8f6f\u4ef6\u662fGaussian\uff0c\u4e8c\u8005\u540c\u5b97\u540c\u6e90\uff0c\u6709\u8bb8\u591a\u76f8\u4f3c\u4e4b\u5904\uff0c\u4e3a\u4e86\u65b9\u4fbfGaussian\u7528\u6237\u5feb\u901f\u4e0a\u624bQ-Chem\uff0c\u7b14\u8005\u6574\u7406\u4e86\u4e00\u4e9b\u5e38\u7528\u5173\u952e\u8bcd\u7684\u5bf9\u7167\u8868\u53ef\u4f9b\u67e5\u8be2(https:\/\/www.homechemer.com\/computchem\/2<\/a>)\u3002Q-Chem\u7a0b\u5e8f\u8ba1\u7b97\u4e59\u70efPY-MECP\u7684\u8f93\u5165\u6587\u4ef6\u5982\u4e0b\uff1a<\/p>\n\n\n\n

\n$molecule\n0 3\n C                 -2.39240544    1.11077629    1.02316771\n C                 -1.06648944    1.11077629    1.02316771\n H                 -2.98599044    0.45738417    0.36977276\n H                 -2.98602144    1.76413589    1.67656125\n H                 -0.94047700    2.00850459    0.78262422\n H                 -0.26589009    1.10234599    1.77493327\n$end\n\n$rem\n    GUI 2\n    JobType Opt\n    Method BHHLYP\n    Basis 6-31G(d,p)\n    MECP_Opt True\n    Spin_Flip True\n    CIS_N_Roots 5\n    MECP_State1 [0,1]\n    MECP_State2 [0,2]\n    MECP_Methods Penalty_Function\n$end\n\n<\/code><\/pre>\n\n\n\n
\u9700\u8981\u6ce8\u610f\u7684\u662f\uff0cMECP\u4f18\u5316\u663e\u8457\u4f9d\u8d56\u4e8e\u521d\u59cb\u7ed3\u6784\u3002\u5408\u7406\u7684\u521d\u59cb\u7ed3\u6784\u6709\u52a9\u4e8e\u6536\u655b\u5230\u610f\u4e49\u660e\u786e\u7684MECP\u7ed3\u6784\uff0c\u5982\u521d\u59cb\u7ed3\u6784\u504f\u79bb\u8f83\u5927\uff0c\u53ef\u80fd\u4f1a\u6536\u655b\u5230CI\u7a7a\u95f4\u5185\u7684\u5176\u4ed6MECP\u7ed3\u6784\uff0c\u5176\u5316\u5b66\u610f\u4e49\u672a\u5fc5\u660e\u786e\u3002\u7528IQMol\u6253\u5f00\u8f93\u51fa\u6587\u4ef6\uff0c\u53ef\u4ee5\u770b\u5230\u6700\u7ec8\u4f18\u5316\u5f97\u5230\u7684\u7ed3\u6784\u5e76\u4e0d\u662fD2d<\/sub>\u7fa4\uff0c\u5404C-H\u952e\u5747\u53d1\u751f\u4e86\u4e00\u5b9a\u7684\u6784\u8c61\u8c03\u6574\u3002\u4e5f\u53ef\u4ee5\u4ece\u8f93\u51fa\u6587\u4ef6\u4e2d\u590d\u5236\u6700\u540e\u4e00\u5e27\u7ed3\u6784\uff0c\u624b\u52a8\u6539\u6210Gaussian\u7684\u8f93\u5165\u6587\u4ef6\u7528GaussView\u67e5\u770b\u3002<\/p>\n\n\n\n
\u7528\u6587\u672c\u7f16\u8f91\u5668\u6253\u5f00\u8f93\u51fa\u6587\u4ef6\u67e5\u770b\u4f18\u5316\u8fc7\u7a0b\u7684\u8f93\u51fa\uff0c\u53ef\u4ee5\u770b\u5230\u9996\u5148\u8fdb\u884c\u4e00\u6b21\u4e09\u91cd\u6001\u57fa\u6001\u7684SCF\u8ba1\u7b97\uff0c\u6536\u655b\u7ed3\u679c\u7684\u81ea\u65cb\u5e73\u65b9\u7b97\u7b26\u671f\u671b\u503c\u4e3a2.004\u3002<\/p>\n\n\n\n
\n A unrestricted SCF calculation will be\n performed using DIIS\n SCF converges when DIIS error is below 1.0e-08\n ---------------------------------------\n  Cycle       Energy         DIIS error\n ---------------------------------------\n    1     -78.8706291302      4.96e-02  \n    2     -78.3339923163      4.72e-03  \n... ...\n   12     -78.3717577980      1.35e-08  \n   13     -78.3717577980      3.37e-09  Convergence criterion met\n ---------------------------------------\n SCF time:   CPU 14.92s  wall 1.00s \n<S^2> =          2.004181205\n SCF   energy in the final basis set =      -78.3717577980\n Total energy in the final basis set =      -78.3717577980\n\n<\/code><\/pre>\n\n\n\n
\u7136\u540e\u8fdb\u884c\u6fc0\u53d1\u7ec4\u6001\u7684\u8fed\u4ee3\uff0c\u8f93\u51faSF-TDDFT\u8ba1\u7b97\u5f97\u5230\u7684\u6fc0\u53d1\u6001\u4fe1\u606f\u3002\u7b2c\u4e00\u6fc0\u53d1\u6001\u7684\u81ea\u65cb\u5e73\u65b9\u7b97\u7b26\u671f\u671b\u503c\u4e3a0.0236\uff0c\u53ef\u4ee5\u6307\u8ba4\u4e3a\u5355\u91cd\u6001\u3002\u7531\u4e8e\u521d\u59cb\u7ed3\u6784\u5e76\u4e0d\u662f\u4e59\u70ef\u7684\u5e73\u9762\u7ed3\u6784\uff0c\u6545\u6b64\u65f6\u57fa\u6001\u5e76\u4e0d\u662f\\pi^2<\/span>\u7ec4\u6001\uff0c\u800c\u662f^3\\pi^1\\pi^{*1}<\/span>\u4e09\u91cd\u6001\uff0c\u5373\u5e73\u9762\u7ed3\u6784\u4e0b\u7684T1<\/sub>\u6001\u3002\u6b64\u65f6\u7684S1<\/sub>\u5373\u4e3a\u5e73\u9762\u7ed3\u6784\u4e0b\u7684S0<\/sub>\u6001\uff0c\u76f8\u5e94\u5730\u6709\u7b2c\u4e09\u6fc0\u53d1\u6001\u4e3aS2<\/sub>\uff0c\u5bf9\u5e94\u4e8e\u5e73\u9762\u7ed3\u6784\u4e0b\u7684S1<\/sub>\u3002\u7b2c\u4e94\u6fc0\u53d1\u6001\u7684\u81ea\u65cb\u5e73\u65b9\u7b97\u7b26\u671f\u671b\u503c\u4e3a0.9960\uff0c\u6709\u663e\u8457\u7684\u81ea\u65cb\u6c61\u67d3\uff0c\u867d\u7136Q-Chem\u9ed8\u8ba41.20\u4e3a\u5224\u65ad\u5355\u91cd\u6001\u548c\u4e09\u91cd\u6001\u7684\u9608\u503c\uff0c\u4f46\u81ea\u65cb\u6c61\u67d3\u4e25\u91cd\u7684\u60c5\u51b5\u8bf4\u660e\u5df2\u7ecf\u4e0d\u9002\u5408\u4f7f\u7528SF-TDDFT\uff0c\u6b64\u65f6\u7684\u7ed3\u679c\u53ef\u80fd\u5e76\u4e0d\u53ef\u9760\uff0c\u5e94\u8be5\u4f7f\u7528CASSCF\u7b49\u65b9\u6cd5\u5bfb\u627e\u4ea4\u53c9\u70b9\u3002\u6b64\u5904\u7b2c\u4e94\u6fc0\u53d1\u6001\u7684\u6fc0\u53d1\u80fd\u8fdc\u9ad8\u4e8e\u7b2c\u4e00\u548c\u7b2c\u4e09\u6fc0\u53d1\u6001\uff0c\u6545\u57fa\u672c\u4e0d\u4f1a\u5f71\u54cd\u7ed3\u679c\uff0c\u53ef\u4ee5\u5ffd\u7565\u3002\u5982\u679c\u5728\u4f18\u5316\u8fc7\u7a0b\u4e2d\u51fa\u73b0\u88ab\u8ddf\u8e2a\u7684\u4e24\u6001\u81ea\u65cb\u6c61\u67d3\u4e25\u91cd\uff0c\u5e94\u8be5\u53ca\u65f6\u505c\u6b62\u8ba1\u7b97\uff0c\u68c0\u67e5\u539f\u56e0\uff0c\u6216\u6362\u7528\u5176\u4ed6\u65b9\u6cd5\uff0c\u4e00\u822c0.50\u4ee5\u4e0b\u7684\u81ea\u65cb\u6c61\u67d3\u90fd\u53ef\u4ee5\u5ffd\u7565\u3002Q-Chem\u4e5f\u652f\u6301\u65e0\u81ea\u65cb\u6c61\u67d3\u7684spin-adapted spin-flip TDDFT (SA-SF-TDDFT)\uff0c\u4f46\u7ecf\u9a8c\u8868\u660eSF-TDDFT\u65e0\u6cd5\u7814\u7a76\u7684\u95ee\u9898\u4e00\u822cSA-SF-TDDFT\u4e5f\u65e0\u6cd5\u7ed9\u51fa\u53ef\u9760\u7ed3\u679c\uff0c\u4e14\u540e\u8005\u6ca1\u6709\u89e3\u6790\u5bfc\u6570\uff0c\u65e0\u6cd5\u8fdb\u884c\u8f83\u5927\u4f53\u7cfb\u7684\u7ed3\u6784\u4f18\u5316\u8ba1\u7b97\u3002<\/p>\n\n\n\n
\n ---------------------------------------------------\n            SF-DFT Excitation Energies              \n (The first \"excited\" state might be the ground state) \n ---------------------------------------------------\n\n Excited state   1: excitation energy (eV) =    0.6403\n Total energy for state  1:                   -78.34822842 au\n    <S**2>     :  0.0236\n    S(    1) --> S(    1) amplitude =  0.4762 alpha\n    S(    1) --> S(    2) amplitude =  0.1888 alpha\n    S(    2) --> S(    1) amplitude =  0.6421 alpha\n    S(    2) --> S(    2) amplitude = -0.5411 alpha\n\n Excited state   2: excitation energy (eV) =    0.8027\n Total energy for state  2:                   -78.34226003 au\n    <S**2>     :  2.0024\n    S(    1) --> S(    1) amplitude =  0.7205 alpha\n    S(    2) --> S(    2) amplitude =  0.6639 alpha\n\n Excited state   3: excitation energy (eV) =    2.0076\n Total energy for state  3:                   -78.29797913 au\n    <S**2>     :  0.0734\n    S(    1) --> S(    1) amplitude = -0.4295 alpha\n    S(    2) --> S(    1) amplitude =  0.7558 alpha\n    S(    2) --> S(    2) amplitude =  0.4664 alpha\n\n Excited state   4: excitation energy (eV) =    4.3458\n Total energy for state  4:                   -78.21205250 au\n    <S**2>     :  0.0946\n    S(    1) --> S(    1) amplitude = -0.1710 alpha\n    S(    1) --> S(    2) amplitude =  0.9682 alpha\n\n Excited state   5: excitation energy (eV) =    7.2166\n Total energy for state  5:                   -78.10655438 au\n    <S**2>     :  0.9960\n    D(    6) --> S(    1) amplitude = -0.2326\n    D(    7) --> S(    1) amplitude = -0.6558\n    S(    2) --> V(    1) amplitude =  0.6627 alpha\n    S(    2) --> V(    2) amplitude =  0.1619 alpha\n\n<\/code><\/pre>\n\n\n\n
\u7136\u540e\u8fdb\u884c\u5f1b\u8c6b\u5bc6\u5ea6\u7684\u8ba1\u7b97\uff0c\u63a5\u7740Q-Chem\u8f93\u51fa\u6709\u5173\u57fa\u6001\u6ce2\u51fd\u6570\u7684\u4e00\u4e9b\u57fa\u672c\u4fe1\u606f\uff0c\u5b8c\u6210\u4e00\u6b21SF-TDDFT\u7684\u5355\u70b9\u8ba1\u7b97\u3002<\/p>\n\n\n\n
\u63a5\u4e0b\u6765\u8fdb\u884c\u68af\u5ea6\u8ba1\u7b97\u3002\u9996\u5148\u6839\u636e\u9608\u503c\u9009\u62e9\u88ab\u8003\u5bdf\u7684\u4e24\u4e2a\u5355\u91cd\u6001\uff1aA threshold of <S**2> = 1.20 is used to identify singlet states\uff0c\u53ef\u901a\u8fc7\u5173\u952e\u8bcdCIS_S2_Thresh N<\/mark> (Threshold: N<\/em>\/100)\u6765\u4eba\u4e3a\u6539\u53d8\u8fd9\u4e00\u9608\u503c\u3002\u7a0b\u5e8f\u8f93\u51fa\u4e24\u6001\u7684\u57fa\u672c\u4fe1\u606f\u53ca\u5f53\u524d\u7ed3\u6784\u4e0b\u4e24\u6001\u7684\u68af\u5ea6\u77e2\u91cf\u3002<\/p>\n\n\n\n
\n calculating CIS gradients for MECP_OPT \r\nWe are using <S**2> to determine which singlet excited state is the target state.\r\nDetermine which singlet state to optimize in UCIS or Spin-Flip UCIS\r\nA threshold of <S**2> = 1.20 is used to identify singlet states\r\n\tExcited state 1, <S^2> = 0.0236: is it a singlet? YES.\ncis_state_deriv: 1\n CIS relaxed dipole moment\n            1\n    1   0.0261541\n    2  -0.3558981\n    3  -0.0619512\n\tMagnitude:\t 0.362 au\t 0.921 Debye\n CIS 1 State Energy is  -78.3482284193\n Gradient of the state energy (including CIS Excitation Energy)\n            1           2           3           4           5           6\n    1  -0.1111696   0.0670777   0.0022334   0.0047943   0.0427766  -0.0057124\n    2  -0.0236528  -0.0465356   0.0075451  -0.0041807   0.1088581  -0.0420340\n    3  -0.0276008  -0.0882929  -0.0261074   0.0307093   0.1318372  -0.0205453\nWe are using <S**2> to determine which singlet excited state is the target state.\nDetermine which singlet state to optimize in UCIS or Spin-Flip UCIS\nA threshold of <S**2> = 1.20 is used to identify singlet states\n\tExcited state 1, <S^2> = 0.0236: is it a singlet? YES.\n\tExcited state 2, <S^2> = 2.0024: is it a singlet? No.\n\tExcited state 3, <S^2> = 0.0734: is it a singlet? YES.\ncis_state_deriv: 3\n CIS relaxed dipole moment\n            1\n    1   0.7909756\n    2  -0.6351955\n    3   0.0093171\n\tMagnitude:\t 1.014 au\t 2.579 Debye\n CIS 3 State Energy is  -78.2979791254\n Gradient of the state energy (including CIS Excitation Energy)\n            1           2           3           4           5           6\n    1  -0.0273931   0.0303176  -0.0014504  -0.0147586   0.0419712  -0.0286867\n    2   0.0259754  -0.1178143   0.0074983  -0.0027563   0.0588073   0.0282896\n    3  -0.0381684  -0.1256791   0.0297313  -0.0245972   0.1740429  -0.0153295\n\n<\/code><\/pre>\n\n\n\n
\u8be5\u4efb\u52a1\u8f93\u5165\u4e2d\u6307\u5b9a\u4e86\u4f7f\u7528\u60e9\u7f5a\u51fd\u6570(penalty function)\u65b9\u6cd5\u4f18\u5316MECP\u70b9\uff0c\u63a5\u4e0b\u6765\u8ba1\u7b97\u60e9\u7f5a\u51fd\u6570\u7b49\u4fe1\u606f\u3002Q-Chem\u6ca1\u6709\u73b0\u6210\u7684\u5173\u952e\u8bcd\u53ef\u4ee5\u4fee\u6539\u60e9\u7f5a\u51fd\u6570\u65b9\u6cd5\u7684\u6536\u655b\u6807\u51c6\uff08\u81f3\u5c11\u624b\u518c\u4e2d\u6ca1\u6709\u7ed9\u51fa\uff09\uff0c\u4f46\u4ece\u7ecf\u9a8c\u770b\u6765\u60e9\u7f5a\u51fd\u6570\u65b9\u6cd5\u6536\u655b\u7cbe\u5ea6\u5e76\u4e0d\u9ad8\uff0c\u4f46\u901f\u5ea6\u4e0a\u5177\u6709\u4e00\u5b9a\u4f18\u52bf\uff0c\u53ef\u4ee5\u5728\u7ed3\u6784\u504f\u79bb\u8f83\u5927\u7684\u60c5\u51b5\u4e0b\u7528\u6765\u505a\u521d\u6b65\u4f18\u5316\u3002\u7136\u540e\u7a0b\u5e8f\u7ed9\u51fa\u7b2c\u4e00\u8f6e\u4f18\u5316\u7684\u7ed3\u679c\u3002\u6700\u540e\u8f93\u51fa\u7684\u6536\u655b\u60c5\u51b5\u4e3a3\u4e2aNO\uff0c\u8bf4\u660e\u79bb\u4f18\u5316\u6536\u655b\u8fd8\u5dee\u5f97\u5f88\u8fdc\u3002<\/p>\n\n\n\n
\n** GEOMETRY OPTIMIZATION IN DELOCALIZED INTERNAL COORDINATES **\n   Searching for a Minimum\n\n   Optimization Cycle:   1\n\n                       Coordinates (Angstroms)\n     ATOM                X               Y               Z\n      1  C         0.6490763685   -0.0166246091    0.0267772021\n      2  C        -0.6664681152    0.1458842232   -0.0046366466\n      3  H         1.3527261412    0.8242369730   -0.0366118550\n      4  H         1.1233438183   -1.0029680196    0.1183135498\n      5  H        -0.8385958381   -0.3674310196   -0.7704929744\n      6  H        -1.5331236410   -0.2293956186    0.5559479467\n   Point Group: c1    Number of degrees of freedom:    12\n\n\n   Energy is    -78.323103772\n\n\n Attempting to generate delocalized internal coordinates\n Initial Hessian constructed with Jon Baker's OPTIMIZE code\n\n 12 Hessian modes will be used to form the next step\n  Hessian Eigenvalues:\n     0.032207    0.032207    0.058678    0.160000    0.160000    0.160000\n     0.160000    0.338745    0.338749    0.338749    0.604807    0.605119\n\n Minimum search - taking simple RFO step\n Searching for Lamda that Minimizes Along All modes\n Value Taken    Lamda =  -0.46930849\n Calculated Step too Large.  Step scaled by  0.336864\n Step Taken.  Stepsize is  0.300000\n\n                             Maximum     Tolerance    Cnvgd?\n         Gradient           0.280807      0.000300      NO\n         Displacement       0.156529      0.001200      NO\n         Energy change     *********      0.000001      NO\n\n<\/code><\/pre>\n\n\n\n
\u4f18\u5316\u6536\u655b\u540e\u8f93\u51fa\u7ed3\u679c\u5982\u4e0b\uff0c\u53ef\u4ee5\u76f4\u63a5\u7528IQMol\u67e5\u770b\uff0c\u6216\u8005\u590d\u5236\u8fd9\u4e00\u7ed3\u6784\u5e76\u5c06\u5176\u6539\u5199\u6210\u5176\u4ed6\u53ef\u89c6\u5316\u7a0b\u5e8f\u53ef\u8bc6\u522b\u7684\u683c\u5f0f\uff0c\u7528\u5176\u4ed6\u7a0b\u5e8f\u67e5\u770b\u3002<\/p>\n\n\n\n
\n ******************************\n **  OPTIMIZATION CONVERGED  **\n ******************************\n\n                       Coordinates (Angstroms)\n     ATOM                X               Y               Z\n      1  C         0.6076202045    0.0099562520    0.0711311781\n      2  C        -0.7414129227    0.3051250047   -0.0214996635\n      3  H         1.3765169742    0.7735724304   -0.0381247666\n      4  H         1.0503425185   -0.9911489616    0.1520435281\n      5  H        -0.8384996307   -0.4170582242   -0.8981561847\n      6  H        -1.3676084101   -0.3267445721    0.6239031312\n\n<\/code><\/pre>\n\n\n\n
\u6ce8\u610f\u67e5\u770b\u6700\u540e\u4e00\u6b21\u8f93\u51fa\u7684SF-TDDFT\u7ed3\u679c\uff0c\u68c0\u67e5\u662f\u5426\u5408\u7406\u3002\u5bf9\u4e8e\u672c\u4f8b\uff0c\u6700\u540e\u4e00\u6b65\u8f93\u51fa\u7684\u7ed3\u679c\u663e\u793a\u7b2c\u4e8c\u548c\u7b2c\u4e09\u6fc0\u53d1\u6001\u4e3a\u88ab\u8003\u5bdf\u7684\u4e24\u4e2a\u5355\u91cd\u6001\uff0c\u81ea\u65cb\u6c61\u67d3\u4e0d\u4e25\u91cd\uff0c\u8bf4\u660eSF-TDDFT\u80fd\u591f\u57fa\u672c\u6b63\u786e\u5730\u7ed9\u51fa\u7ed3\u679c\u3002\u4e24\u6001\u6fc0\u53d1\u80fd\u5206\u522b\u4e3a0.9202 eV\u548c0.9346 eV\uff0c\u6bd4\u8f83\u63a5\u8fd1\uff0c\u4f46\u4ecd\u6709\u4e00\u5b9a\u80fd\u9699\uff0c\u8fd9\u662f\u56e0\u4e3aQ-Chem\u4e2d\u60e9\u7f5a\u51fd\u6570\u65b9\u6cd5\u9ed8\u8ba4\u7684\u6536\u655b\u7cbe\u5ea6\u4e0d\u591f\u9ad8\u6240\u81f4\uff0c\u53ef\u4ee5\u5728\u60e9\u7f5a\u51fd\u6570\u65b9\u6cd5\u7684\u4f18\u5316\u57fa\u7840\u4e0a\u7ee7\u7eed\u7528\u5206\u652f\u5e73\u9762\u9012\u63a8\u65b9\u6cd5(branching plane updating method, BPUPD)\u8fdb\u4e00\u6b65\u4f18\u5316\uff0c\u5173\u952e\u8bcd\u4e3aMECP_Methods Branching_Plane<\/mark>\u3002<\/p>\n\n\n\n
\n ---------------------------------------------------\n            SF-DFT Excitation Energies              \n (The first \"excited\" state might be the ground state) \n ---------------------------------------------------\n\n Excited state   1: excitation energy (eV) =    0.8273\n Total energy for state  1:                   -78.35539548 au\n    <S**2>     :  1.7606\n    S(    1) --> S(    1) amplitude =  0.3977 alpha\n    S(    2) --> S(    2) amplitude =  0.8950 alpha\n\n Excited state   2: excitation energy (eV) =    0.9202\n Total energy for state  2:                   -78.35197980 au\n    <S**2>     :  0.2504\n    S(    1) --> S(    1) amplitude =  0.8678 alpha\n    S(    2) --> S(    2) amplitude = -0.4047 alpha\n\n Excited state   3: excitation energy (eV) =    0.9346\n Total energy for state  3:                   -78.35145141 au\n    <S**2>     :  0.0974\n    S(    2) --> S(    1) amplitude =  0.9829 alpha\n\n Excited state   4: excitation energy (eV) =    5.6717\n Total energy for state  4:                   -78.17736611 au\n    <S**2>     :  0.1993\n    S(    1) --> S(    2) amplitude =  0.9757 alpha\n\n Excited state   5: excitation energy (eV) =    6.0180\n Total energy for state  5:                   -78.16464165 au\n    <S**2>     :  0.9844\n    D(    5) --> S(    1) amplitude = -0.1790\n    D(    7) --> S(    1) amplitude =  0.9317\n    S(    2) --> V(    1) amplitude =  0.1706 alpha\n\n<\/code><\/pre>\n\n\n\n
\u7c7b\u4f3c\u5730\u4e5f\u53ef\u4ee5\u4f7f\u7528SF-TDDFT\u4f18\u5316\u4e59\u70ef\u5176\u4ed6\u7684\u4e24\u4e2aMECP\u7ed3\u6784\u3002<\/p>\n\n\n\n
3.2 \u5076\u6c2e\u82ef<\/strong><\/p>\n\n\n\n
\u5076\u6c2e\u82ef\u884d\u751f\u7269\u4e5f\u662f\u5178\u578b\u7684\u5149\u5f02\u6784\u5316\u4f53\u7cfb\uff0c\u5149\u7167\u53ef\u4ee5\u5f15\u53d1N=N\u65cb\u8f6c\uff0c\u7ecf\u8fc7\u5706\u9525\u4ea4\u53c9\u7a7a\u95f4\u53d1\u751f\u65e0\u8f90\u5c04\u9000\u6fc0\u3002\u5bf9\u4e8e\u4e59\u70ef\u7684\u4f8b\u5b50\uff0c\u53cd\u5e94\u7269\u548c\u5149\u4ea7\u7269\u76f8\u540c\uff0c\u57fa\u6001\u52bf\u80fd\u9762\u662f\u5bf9\u79f0\u7684\uff0c\u800c\u5bf9\u4e8e\u672c\u4f8b\u57fa\u6001\u52bf\u80fd\u9762\u662f\u4e0d\u5bf9\u79f0\u7684\uff0c\u5076\u6c2e\u82ef\u7684\u53cd\u5f0f\u6784\u578b\u66f4\u7a33\u5b9a\u3002<\/p>\n\n\n
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\"\"<\/figure>\n<\/div>\n\n\n
\u8fd9\u91cc\u4f7f\u7528BPUPD\u65b9\u6cd5\u5bfb\u627eMECP\u3002\u9700\u8981\u6ce8\u610f\u7684\u662f\uff0cBPUPD\u65b9\u6cd5\u5bfb\u627eMECP\u5fc5\u987b\u5728\u7b1b\u5361\u5c14\u5750\u6807\u7cfb\u4e0b\u8fdb\u884c\uff0c\u8f93\u5165\u6587\u4ef6\u4e2d\u5fc5\u987b\u58f0\u660eGeom_Opt_Coords 0<\/mark>\u3002<\/p>\n\n\n\n
\n$molecule\n0 3\n C      -4.0110072727     0.8867526059     0.3687781802\n C      -3.8222885520     0.1505268061    -0.7936223690\n C      -2.6476065948    -0.5326805745    -1.0177433591\n C      -1.6206000793    -0.4914864252    -0.0630824037\n C      -1.8025446291     0.2696971939     1.1048807371\n C      -2.9921416581     0.9396982830     1.3075866152\n H      -4.9389392307     1.4045952162     0.5425163975\n H      -4.6023457015     0.1088998387    -1.5365103065\n H      -2.4981195408    -1.1066786311    -1.9158632277\n H      -1.0117017289     0.3146118162     1.8336312773\n H      -3.1220771286     1.5114085108     2.2141869803\n N      -0.4855558694    -1.1909791741    -0.2754674856\n N       0.5912930884    -1.4021822808     0.3187355517\n C       1.6830154825    -0.5736601800     0.0500793982\n C       2.8250095993    -0.7988856552     0.8166873615\n C       1.6672547417     0.4438601437    -0.9078788565\n C       3.9293339675     0.0128224074     0.6567958452\n H       2.8080105108    -1.5984694578     1.5366698658\n C       2.7831903508     1.2382719085    -1.0704928250\n H       0.7876846961     0.5858991456    -1.5116494451\n C       3.9108653261     1.0314856400    -0.2852427246\n H       4.8062044477    -0.1459567658     1.2605555974\n H       2.7786628938     2.0217713704    -1.8113373491\n H       4.7759979864     1.6594860134    -0.4170191124\n$end\n\n$rem\n    GUI 2\n    JobType Opt\n    Geom_Opt_DMax 50\n    Geom_Opt_Coords 0\n    Method BHHLYP\n    Basis 6-31G(d,p)\n    Spin_Flip True\n    CIS_N_Roots 5\n    MECP_Opt True\n    MECP_State1 [0,1]\n    MECP_State2 [0,2]\n    MECP_Methods Branching_Plane\n$end\n\n<\/code><\/pre>\n\n\n\n
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