乐胖代购免代理版

{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,5,2]],"date-time":"2025-05-02T12:52:47Z","timestamp":1746190367441},"reference-count":51,"publisher":"Wiley","issue":"14","license":[{"start":{"date-parts":[[2009,4,6]],"date-time":"2009-04-06T00:00:00Z","timestamp":1238976000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2009,11,15]]},"abstract":"Abstract<\/jats:title>The importance of basis sets and active spaces in the determination of the potential energy curves and relevant energy differences in the Oh<\/jats:italic><\/jats:sub>\u2010symmetry model system [Fe(NCH)6<\/jats:sub>]2+<\/jats:sup> is analyzed using the Complete Active Space Self\u2010Consistent Field (CASSCF) method and subsequent second\u2010order perturbative treatment (CASPT2). By comparison of a series of atomic basis sets contraction, it is concluded that a balanced description of the Fe 7s<\/jats:italic>6p<\/jats:italic>5d<\/jats:italic>3f<\/jats:italic>2g<\/jats:italic>1h<\/jats:italic> and N 4s<\/jats:italic>3p<\/jats:italic>1d<\/jats:italic> partners is needed to reach convergence upon the potential energy surface descriptions. Since the spin\u2010crossover phenomenon involves the simultaneous change in the spin nature and expansion of the coordination sphere of the metal ion (i.e.,<\/jats:italic> lengthening of the Fe\u2010N distances), the standard 10 electrons\/12 orbitals complete active space is confronted to a chemically intuitive 18 electrons\/15 orbitals picture. The role of a second d<\/jats:italic>\u2010shell is finally examined using the extended RAS strategy. Using a valence\u2010bond type analysis, it is shown that the so\u2010called d<\/jats:italic>\u2032<\/jats:sup> orbitals allow for a significant charge redistribution (\u223c0.5 electron) along the transition. Our calculations are compared to reference coupled\u2010cluster estimations. \u00a9 2009 Wiley Periodicals, Inc. J Comput Chem, 2009<\/jats:p>","DOI":"10.1002\/jcc.21236","type":"journal-article","created":{"date-parts":[[2009,4,6]],"date-time":"2009-04-06T14:34:05Z","timestamp":1239028445000},"page":"2327-2333","source":"Crossref","is-referenced-by-count":73,"title":["Energetics of [Fe(NCH)_{6<\/sub>]^{2+<\/sup> via CASPT2 calculations: A spin\u2010crossover perspective"],"prefix":"10.1002","volume":"30","author":[{"given":"Mika\u00ebl","family":"Kepenekian","sequence":"first","affiliation":[]},{"given":"Vincent","family":"Robert","sequence":"additional","affiliation":[]},{"given":"Boris","family":"Le Guennic","sequence":"additional","affiliation":[]},{"given":"Coen","family":"De Graaf","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2009,8,24]]},"reference":[{"key":"e_1_2_6_2_2","series-title":"Topics in Current Chemistry","author":"G\u00fctlich P.","year":"2004"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.279.5347.44"},{"key":"e_1_2_6_4_2","volume-title":"Molecular Magnetism","author":"Kahn O.","year":"1993"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00220-5"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1007\/b95427"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp051958p"},{"key":"e_1_2_6_8_2","first-page":"199","volume":"235","author":"Paulsen H.","year":"2004","journal-title":"Top Curr Chem"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp026586o"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic025891l"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(03)00028-9"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/jrs.1437"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic971174t"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200500972"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic701352c"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(93)80104-H"},{"key":"e_1_2_6_17_2","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1016\/S0009-2614(97)01073-7","volume":"281","author":"Garcia V. M.","year":"1997","journal-title":"Chem Phys Lett"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.476587"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.63.014404"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1080\/00268970110105433"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja030124m"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic051526t"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic701758x"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2007.12.005"},{"key":"e_1_2_6_25_2","series-title":"Principles and Applications of Density Functional Theory in Inorganic Chemistry I","first-page":"151","author":"Harvey J. N.","year":"2004"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp074480t"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2406067"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.78.024433"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1710046"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1839854"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2353829"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2820786"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja804506h"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja805626s"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp982759r"},{"key":"e_1_2_6_36_2","volume-title":"Introduction to Ligand Field Theory","author":"Ballhausen C. J.","year":"1962"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.75.165116"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2715552"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2920188"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100377a012"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.462209"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0927-0256(03)00109-5"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(97)00669-6"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2004.08.032"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1016\/0003-4916(74)90333-9"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.33.3742"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp031064"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0581126"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.439529"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.442456"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.455063"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(96)00083-3"}],"container-title":["Journal of Computational Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fjcc.21236","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/jcc.21236","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,28]],"date-time":"2023-09-28T15:28:13Z","timestamp":1695914893000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/jcc.21236"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,8,24]]},"references-count":51,"journal-issue":{"issue":"14","published-print":{"date-parts":[[2009,11,15]]}},"alternative-id":["10.1002\/jcc.21236"],"URL":"https:\/\/doi.org\/10.1002\/jcc.21236","archive":["Portico"],"relation":{},"ISSN":["0192-8651","1096-987X"],"issn-type":[{"value":"0192-8651","type":"print"},{"value":"1096-987X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,8,24]]}}}}}