論文

査読有り
2010年9月

Quantum Mechanical Reaction Probability of Triplet Ketene at the Multireference Second-Order Perturbation Level of Theory

JOURNAL OF PHYSICAL CHEMISTRY A
  • Yusuke Ogihara
  • ,
  • Takeshi Yamamoto
  • ,
  • Shigeki Kato

114
37
開始ページ
9981
終了ページ
9990
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/jp104089m
出版者・発行元
AMER CHEMICAL SOC

Triplet ketene exhibits a steplike structure in the experimentally observed dissociation rates, but its mechanism is still unknown despite many theoretical efforts in the past decades. In this paper we revisit this problem by quantum mechanically calculating the reaction probability with multireference-based electronic structure theory. Specifically, we first construct an analytical potential energy surface of triplet state by fitting it to about 6000 ab initio energies computed at the multireference second-order Moller-Plesset perturbation (MRMP2) level. We then evaluate the cumulative reaction probability by using the transition state wave packet method together with an adiabatically constrained Hamiltonian. The result shows that the imaginary barrier frequency on the triplet surface is 328i cm(-1), which is close to the CCSD(T) result (321i cm(-1)) but is likely too large for reproducing the experimentally observed steps. Indeed, our calculated reaction probability exhibits no signature of steps, reflecting too strong tunneling effect along the reaction coordinate. Nevertheless, it is emphasized that the flatness of the potential profile in the transition-state region (which governs the degree of tunneling) depends strongly on the level of electronic structure calculation, thus leaving some possibility that the use of more accurate theories might lead to the observed steps. We also demonstrate that the triplet potential surface differs significantly between the CASSCF and MRMP2 results, particularly in the transition-state region. This fact seems to require more attention when studying the "nonadiabatic" scenario for the steps, in which the crossing seam between S(0) and T(1) surfaces is assumed to play a central role.

リンク情報
DOI
https://doi.org/10.1021/jp104089m
PubMed
https://www.ncbi.nlm.nih.gov/pubmed/20722429
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000281753800003&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/jp104089m
  • ISSN : 1089-5639
  • PubMed ID : 20722429
  • Web of Science ID : WOS:000281753800003

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