AB-INITIO POTENTIAL-ENERGY SURFACE AND NEAR-INFRARED SPECTRUM OF THE HE-C2H2 COMPLEX

被引:69
作者
MOSZYNSKI, R [1 ]
WORMER, PES [1 ]
VANDERAVOIRD, A [1 ]
机构
[1] UNIV WARSAW, DEPT CHEM, PL-02093 WARSAW, POLAND
关键词
D O I
10.1063/1.468830
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
Symmetry-adapted perturbation theory has been applied to compute the intermolecular potential energy surface of the He-C2H2 complex. The interaction energy is found to be dominated by the first-order exchange contribution and the dispersion energy. In both contributions it was necessary to include high-level intramolecular correlation effects. Our potential has a global minimum of εm=-22.292 cm-1 near the linear He-HCCH geometry at Rm=8.20 bohr and φm=14. 16°, and a local minimum at a skew geometry (Rm=7.39 bohr, φm=48.82°, and εm=-21.983 cm-1). The computed potential energy surface has been analytically fitted and used in converged variational calculations to generate bound rovibrational states of the He-C2H2 molecule and the near-infrared spectrum, which corresponds to the simultaneous excitation of the vibration and hindered rotation of the C2H2 monomer within the complex. The nature of the bound states and of the spectrum predicted from the ab initio potential are discussed. © 1995 American Institute of Physics.
引用
收藏
页码:8385 / 8397
页数:13
相关论文
共 100 条
[1]   DISTRIBUTED POLARIZABILITIES USING THE TOPOLOGICAL THEORY OF ATOMS IN MOLECULES [J].
ANGYAN, JG ;
JANSEN, G ;
LOOS, M ;
HATTIG, C ;
HESS, BA .
CHEMICAL PHYSICS LETTERS, 1994, 219 (3-4) :267-273
[2]   VIBRATIONALLY RESOLVED INELASTIC-SCATTERING AND CHARGE-TRANSFER IN H+ +C2H2 COLLISIONS [J].
ARISTOV, N ;
NIEDNERSCHATTEBURG, G ;
TOENNIES, JP ;
CHIU, YN .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (11) :7969-7983
[3]   SCATTERING EXPERIMENTS WITH HYDROGEN-ATOMS - VELOCITY DEPENDENCE OF INTEGRAL TOTAL CROSS-SECTION WITH SIMPLE MOLECULES IN ENERGY-RANGE 0.01-1.00 EV (CM) [J].
BAUER, W ;
BICKES, RW ;
LANTZSCH, B ;
TOENNIES, JP ;
WALASCHEWSKI, K .
CHEMICAL PHYSICS LETTERS, 1975, 31 (01) :12-16
[4]   THE AR-C2H2 INTERMOLECULAR POTENTIAL FROM HIGH-RESOLUTION SPECTROSCOPY AND AB-INITIO THEORY - A CASE FOR MULTICENTER INTERACTIONS [J].
BEMISH, RJ ;
BLOCK, PA ;
PEDERSEN, LG ;
YANG, WT ;
MILLER, RE .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (11) :8585-8598
[5]   AR-C2H2 VAN-DER-WAALS DIMER - A PATHOLOGICALLY FLAT POTENTIAL-ENERGY SURFACE [J].
BONE, RGA .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (12) :3126-3138
[6]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[7]   INFRARED SPECTRA OF HIGHLY COMPRESSED GAS MIXTURES OF TYPE HCL+X . A THEORETICAL STUDY [J].
BRATOZ, S ;
MARTIN, ML .
JOURNAL OF CHEMICAL PHYSICS, 1965, 42 (03) :1051-&
[8]  
Brink D. M., 1975, ANGULAR MOMENTUM
[9]   THE ANISOTROPIC INTERACTION OF HE-C2H2 FROM DIFFERENTIAL SCATTERING EXPERIMENTS [J].
BUCK, U ;
ETTISCHER, I ;
SCHLEMMER, S ;
YANG, MB ;
VOHRALIK, P ;
WATTS, RO .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (05) :3494-3502
[10]  
Bunker P. R., 2006, MOL SYMMETRY SPECTRO