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Volumn 16, Issue 7, 2014, Pages 3122-3133

New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations

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EID: 84892729382     PISSN: 14639076     EISSN: None     Source Type: Journal    
DOI: 10.1039/c3cp54418d     Document Type: Article
Times cited : (34)

References (114)
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    • In theory, increasing the size of the active space can allow us to recover a part of the dynamical electronic correlation energy. However, in most cases, this strategy requires an active space too large to be computationally practical
    • C. Gonzalez H. B. Schlegel J. Phys. Chem. 1990 94 5523
    • (1990) J. Phys. Chem. , vol.94 , pp. 5523
    • Gonzalez, C.1    Schlegel, H.B.2
  • 51
    • 79958812733 scopus 로고    scopus 로고
    • It is noteworthy that optimizations of excited state minima and conical intersections of similar compounds at the (MS-)MR-PT2 level of theory were performed in previous studies using numerical optimization procedures. 110-113 The resulting structures and energetics were compared to CASSCF predictions. Overall, this studies suggested that, while it is known that the MS-MR-PT2//CASSCF standard procedure can yield dramatically different results than full CASSCF calculations, both in term of energetics and of mechanistic picture of the process under investigation, full MS-MR-PT2 calculations (both optimizations and potential energy scans) are not expected to significantly alter the conclusions obtained by MS-MR-PT2//CASSCF calculations. We mention, however, that in particularly tricky cases where the ordering of the states is very different from CASSCF to MS-MR-PT2, a full MS-MR-PT2 study can be the only solution to obtain reliable results. 114
    • A. A. Granovsky J. Chem. Phys. 2011 134 214113
    • (2011) J. Chem. Phys. , vol.134 , pp. 214113
    • Granovsky, A.A.1
  • 90
    • 57649146651 scopus 로고    scopus 로고
    • The 1ππ* and 2ππ* states are bound and their energies increase significantly with the N-H bond length. At large N-H bond length, 1ππ* and 2ππ* state potential energy curves cross that of high lying dissociative states, including a number of states dominated by doubly excited configurations. This situation leads to considerable difficulty in keeping track of the states of interest and to convergence problems. Computing separately the A′ and A′′ states was found to greatly simplify the calculation since only crossings implying states of the same symmetry remained to be dealt with
    • O. P. J. Vieuxmaire Z. Lan A. L. Sobolewski W. Domcke J. Chem. Phys. 2008 129 224307
    • (2008) J. Chem. Phys. , vol.129 , pp. 224307
    • Vieuxmaire, O.P.J.1    Lan, Z.2    Sobolewski, A.L.3    Domcke, W.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.