Ab initio calculations on 1,3,5-trimethylenebenzene and its negative ion provide predictions about the photoelectron spectrum of the ion

Journal of the American Chemical Society

Volumn 119, Issue 28, 1997, Pages 6564-6574

  Kemnitz, Carl R ^a   Squires, Robert R ^b   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

^b PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,3,5 TRIMETHYLENEBENZENE; BENZENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; COMPUTER SIMULATION; DRUG STRUCTURE; IONIZATION; MOLECULAR DYNAMICS; PHOTOCHEMISTRY; THEORY;

EID: 0030862875     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970195j     Document Type: Article

References (71)

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46. y″.
47. 1″.
48. 1″.
49. CASSCF calculations do not include any dynamic correlation between σ and π electrons; CASPT2N, by using second-order perturbation theory, exaggerates the effect of dynamic correlation. A CI calculation in which the magnitude of the energy difference between two spin states is correctly computed should thus give an energy separation whose size is intermediate between that computed at the CASSCF and CASPT2N levels.
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53. The twisted geometry is computed to lie higher in energy than the planar structure by 2.5 kcal/mol at CASPT2N/6-31G* and 6.6 kcal/mol at UB3LYP/6-31G*. UB3LYP/6-31G* frequency calculations find the twisted geometry to be the transition state for methylene rotation.
54. 1′ excited state involves an excitation of an electron out of a π bonding orbital into a NBMO or out of a NBMO into an antibonding π orbital.
55. 3h symmetry.
56. 2″ NBMO.
57. 1′ with which it mixes.
58. UB3LYP/6-31+G* calculations place the twisted triplet state 15.4 kcal/mol above the planar geometry.
59. - remain very close to those calculated for 1.
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64. 47b
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70. -.
71. 2E″ state of 1 could be very complex.