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A two‐state reactivity rationale for the reaction of ta atom with acetonitrile in the gas phase
Author(s) -
Ji Dafang,
Wang Yongcheng,
Jin Yanzi,
Lv Lngling,
Wang Cuilan,
Nian Jingyan
Publication year - 2012
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23287
Subject(s) - chemistry , reaction mechanism , acetonitrile , potential energy , computational chemistry , atom (system on chip) , reactivity (psychology) , spin states , spin (aerodynamics) , atomic physics , thermodynamics , physics , catalysis , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology , computer science , embedded system
The spin‐forbidden reaction mechanism of Ta ( 4 F, 5d 3 6s 2 ) with CH 3 CN, on two different potential surfaces (PESs) has been investigated at the B3LYP, MP2, and CCSD level of theory. Crossing points between the PESs are located using different methods, and possible spin inversion processes are discussed by means of spin‐orbit coupling calculations. As a result, the reaction system will change its spin multiplicities near this crossing seam, leading to a significant decrease in the barrier of 2‐4 TS3 from 24.17 to 5.36 kcal/mol, which makes the reaction access to a lower energy pathway and accelerate the reaction rate. © 2012 Wiley Periodicals, Inc.