Reinterpretation of the electronic absorption spectrum of the methylene amidogen radical (H2CN)

被引:1
作者
Abbott, Adam S. [1 ]
Glick, Zach L. [1 ]
Schaefer, Henry F., III [1 ]
机构
[1] Univ Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USA
关键词
CONFIGURATION-INTERACTION CALCULATIONS; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; RELATIVISTIC CORRECTIONS; PERTURBATION-THEORY; EXCITED-STATES; SYSTEMATIC SEQUENCES; ENERGY CORRECTIONS; SPIN-RESONANCE; WAVE-FUNCTIONS;
D O I
10.1063/1.5042763
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The peculiar electronic absorption spectrum of H2CN has been of great interest to experiment. Herein, this system is studied extensively by applying theoretical methods to the ground and low-lying excited electronic states. Employing a large breadth of high-level ab initio computations, including coupled cluster [CCSD(T) and CCSDT(Q)] and multireference configuration interaction [MRCISD+Q] methods, we comprehensively demonstrate that the most recent experimental and theoretical interpretations of the electronic spectrum of H2CN are in error. The previous assignments of the two broad features in the spectrum as the origin 0(0)(0) (similar to 35 050 cm(-1)) and 4(0)(2) (similar to 35 600 cm(-1)) (B) over tilde (2)A(1) <- (X) over tilde B-2(2) transitions are both found to be incorrect. The presently reported transition energies suggest that the higher energy band near 35 600 cm(-1) is the true origin band. Additionally, from the computed anharmonic vibrational frequencies of the (X) over tilde B-2(2) and (B) over tilde (2)A(1) states, we show that this similar to 550 cm(-1) band spacing cannot be attributed to a simple vibronic transition, as claimed by the 4(2)(0) assignment. Possible alternative explanations for the appearance of the lower intensity band near 35 050 cm(-1) are discussed. Published by AIP Publishing.
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页数:8
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共 62 条
  • [1] ELECTRONIC-STRUCTURE AND VERTICAL EXCITATION SPECTRUM OF METHYLENE AMIDOGEN CH2N
    ADAMS, GF
    YARKONY, DR
    BARTLETT, RJ
    PURVIS, GD
    [J]. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1983, 23 (02) : 437 - 446
  • [2] ADAMS GF, 1992, ANNU REV PHYS CHEM, V43, P311
  • [3] NITRAMINE PROPELLANT IGNITION AND COMBUSTION RESEARCH
    ALEXANDER, MH
    DAGDIGIAN, PJ
    JACOX, ME
    KOLB, CE
    MELIUS, CF
    RABITZ, H
    SMOOKE, MD
    TSANG, W
    [J]. PROGRESS IN ENERGY AND COMBUSTION SCIENCE, 1991, 17 (04) : 263 - 296
  • [4] [Anonymous], J CHEM PHYS
  • [5] THEORETICAL-STUDIES OF THE REACTIONS OF HCN WITH ATOMIC-HYDROGEN
    BAIR, RA
    DUNNING, TH
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1985, 82 (05) : 2280 - 2294
  • [6] NONITERATIVE 5TH-ORDER TRIPLE AND QUADRUPLE EXCITATION-ENERGY CORRECTIONS IN CORRELATED METHODS
    BARTLETT, RJ
    WATTS, JD
    KUCHARSKI, SA
    NOGA, J
    [J]. CHEMICAL PHYSICS LETTERS, 1990, 165 (06) : 513 - 522
  • [7] Excited state dynamics of H2CN radicals
    Bernard, EJ
    Strazisar, BR
    Davis, HF
    [J]. CHEMICAL PHYSICS LETTERS, 1999, 313 (3-4) : 461 - 466
  • [8] Coupled-cluster characterization of the ground and excited states of the CH2N and CH2P radicals
    Brinkmann, NR
    Wesolowski, SS
    Schaefer, HF
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (07) : 3055 - 3064
  • [9] Chakraborty D, 2002, J COMPUT-AIDED MATER, V8, P203
  • [10] MOLECULAR-ORBITAL STUDIES OF HYPERFINE COUPLING-CONSTANTS IN THE H2CN AND H(HO)CN RADICALS
    CHIPMAN, DM
    CARMICHAEL, I
    FELLER, D
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (12) : 4702 - 4708