PRECISE SOLUTION OF THE ROTATION BENDING SCHRODINGER EQUATION FOR A TRIATOMIC MOLECULE WITH APPLICATION TO THE WATER MOLECULE

被引:269
作者
HOY, AR [1 ]
BUNKER, PR [1 ]
机构
[1] NATL RES COUNCIL CANADA,HERZBERG INST ASTROPHYS,OTTAWA K1A 0R6,ONTARIO,CANADA
关键词
D O I
10.1016/0022-2852(79)90019-5
中图分类号
O64 [物理化学(理论化学)、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号
070203 ; 070304 ; 081704 ; 1406 ;
摘要
In this paper we report the results of improving the non-rigid bender formulation of the rotation-vibration Hamiltonian of a triatomic molecule [see A. R. Hoy and P. R. Bunker, J. Mol. Spectrosc., 52, 439 (1974)]. This improved Hamiltonian can be diagonalized as before by a combination of numerical integration and matrix diagonalization and it yields rotation-bending energies to high values of the rotational quantum numbers. We have calculated all the rotational energy levels up to J = 10 for the (v1, v2, v3) states (0, 0, 0) and (0, 1, 0) for both H2O and D2O. By least squares fitting to the observations varying seven parameters we have refined the equilibrium structure and force field of the water molecule and have obtained a fit to the 375 experimental energies used with a root mean square deviation of 0.05 cm-1. The equilibrium bond angle and bond length are determined to be 104.48° and 0.9578 Å respectively. We have also calculated these energy levels using the ab initio equilibrium geometry and force constants of Rosenberg, Ermler and Shavitt [J. Chem. Phys., 65, 4072 (1976)] and this is then the first complete ab initio calculation of rotation-vibration energy levels of high J in a polyatomic molecule to this precision. the rms fit of these ab initio energies to the experimental energies for the H2O molecule is 2.65 cm-1. © 1979.
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页码:1 / 8
页数:8
相关论文
共 13 条
[1]   RIGID BENDER AND SEMIRIGID BENDER MODELS FOR ROTATION-VIBRATION HAMILTONIAN [J].
BUNKER, PR ;
LANDSBERG, BM .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1977, 67 (1-3) :374-385
[2]   BENDING-ROTATION HAMILTONIAN FOR TRIATOMIC MOLECULE AND APPLICATION TO HCN AND H2O [J].
BUNKER, PR ;
STONE, JMR .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1972, 41 (02) :310-&
[3]   ZEEMAN EFFECT IN ROTATIONAL SPECTRA OF ASYMMETRIC-ROTOR MOLECULES [J].
BURKE, BF ;
STRANDBERG, MWP .
PHYSICAL REVIEW, 1953, 90 (02) :303-308
[4]   HIGHER RO-VIBRATIONAL LEVELS OF H2O DEDUCED FROM HIGH-RESOLUTION OXYGEN-HYDROGEN FLAME SPECTRA BETWEEN 6200 AND 9100 CM-1 [J].
CAMYPEYRET, C ;
FLAUD, JM ;
MAILLARD, JP ;
GUELACHVILI, G .
MOLECULAR PHYSICS, 1977, 33 (06) :1641-1650
[5]   2UPSILON2, UPSILON1 AND UPSILON3 BANDS OF H2 O-16 ROTATIONAL STUDY OF (000) AND (020) STATES [J].
FLAUD, JM ;
CAMYPEYR.C .
MOLECULAR PHYSICS, 1973, 26 (04) :811-823
[6]   HIGHER RO-VIBRATIONAL LEVELS OF H2O DEDUCED FROM HIGH-RESOLUTION OXYGEN-HYDROGEN FLAME SPECTRA BETWEEN 2800-6200 CM-1 [J].
FLAUD, JM ;
CAMYPEYRET, C ;
MAILLARD, JP .
MOLECULAR PHYSICS, 1976, 32 (02) :499-521
[7]   VIBRATION-ROTATION PROBLEM IN TRIATOMIC MOLECULES ALLOWING FOR A LARGE-AMPLITUDE BENDING VIBRATION [J].
HOUGEN, JT ;
BUNKER, PR ;
JOHNS, JWC .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1970, 34 (01) :136-&
[8]   EFFECTIVE ROTATION-BENDING HAMILTONIAN OF A TRIATOMIC MOLECULE, AND ITS APPLICATION TO EXTREME CENTRIFUGAL-DISTORTION IN WATER MOLECULE [J].
HOY, AR ;
BUNKER, PR .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1974, 52 (03) :439-456
[9]   ANHARMONIC FORCE CONSTANT CALCULATIONS [J].
HOY, AR ;
MILLS, IM ;
STREY, G .
MOLECULAR PHYSICS, 1972, 24 (06) :1265-1290
[10]  
HOY AR, 1976, J MOL SPECTROSC, V59, P159