A DENSITY-FUNCTIONAL STUDY OF M-C2H4 COMPLEXES (M=LI, NA, K) - SINGULARITY OF THE LI ATOM

被引:29
作者
ALIKHANI, ME
HANNACHI, Y
MANCERON, L
BOUTEILLER, Y
机构
[1] UNIV BORDEAUX 1,PHOTOPHYS & PHOTOCHIM MOLEC LAB,CNR,URA 348,F-33405 TALENCE,FRANCE
[2] UNIV PARIS 06,SPECTROCHIM MOLEC LAB,URA 508,PARIS 05,FRANCE
关键词
D O I
10.1063/1.469914
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
Quantum chemical calculations on the Li-C2H4 complex have been performed with coupled-cluster and density functional methods. For both methods the electronic ground state of the complex is calculated to be B-2(2), With a C-2 upsilon symmetry equilibrium structure, and the calculated binding energy is quite small (around 2 kcal/mol), and therefore very much basis set dependent. The vibrational spectrum has been calculated at the harmonic approximation, including C-13/C-12, Li-7/Li-6, and H/D isotopic substitutions. The agreement between experimental and calculated infrared frequencies is correct, except for the low frequency symmetric Li-C stretching mode. These calculations also allow to propose an assignment for the observed C-H/C-D stretching modes. The observed blue-shift of the symmetric CH2 bending mode as well as the red-shift of the antisymmetric CH2 bending, CD2 bending, and C-C stretching modes with respect to the free ethylene have been confirmed by the density functional calculations. The Na ... C2H4 complex has been found to be unstable in its B-2(2) electronic state. The study of the (2)A(1) electronic state for both Na ... C2H4 and K ... C2H4 complexes show that they are at most very weak van der Waals complexes, This result confirms the conclusions of matrix isolation experiments. (C) 1995 American Institute of Physics.
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页码:10128 / 10136
页数:9
相关论文
共 45 条
[11]   SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .25. SUPPLEMENTARY FUNCTIONS FOR GAUSSIAN-BASIS SETS [J].
FRISCH, MJ ;
POPLE, JA ;
BINKLEY, JS .
JOURNAL OF CHEMICAL PHYSICS, 1984, 80 (07) :3265-3269
[12]  
FRISCH MJ, 1995, GAUSSIAN 94 DFT REVI
[13]   THE ISOMERS OF SILACYCLOPROPANE [J].
GORDON, MS .
CHEMICAL PHYSICS LETTERS, 1980, 76 (01) :163-168
[14]   THE HARMONIC FREQUENCIES OF BENZENE [J].
HANDY, NC ;
MASLEN, PE ;
AMOS, RD ;
ANDREWS, JS ;
MURRAY, CW ;
LAMING, GJ .
CHEMICAL PHYSICS LETTERS, 1992, 197 (4-5) :506-515
[15]  
HAY PJ, 1985, J CHEM PHYS, V82, P299, DOI [10.1063/1.448975, 10.1063/1.448799, 10.1063/1.448800]
[16]  
JIN SQ, 1990, CHEM PHYS LETT, V170, P301, DOI 10.1016/0009-2614(90)87132-B
[17]   SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .20. BASIS SET FOR CORRELATED WAVE-FUNCTIONS [J].
KRISHNAN, R ;
BINKLEY, JS ;
SEEGER, R ;
POPLE, JA .
JOURNAL OF CHEMICAL PHYSICS, 1980, 72 (01) :650-654
[18]  
Labanowski J.K., 1991, DENSITY FUNCTIONAL M
[19]   CALCULATED INFRARED FREQUENCIES AND INTENSITIES OF THE HO2 RADICAL [J].
LAUDERDALE, WJ ;
CHENG, VG ;
WIERSCHKE, SG .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (17) :4502-4505
[20]   DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].
LEE, CT ;
YANG, WT ;
PARR, RG .
PHYSICAL REVIEW B, 1988, 37 (02) :785-789