Molecular equilibrium structures from experimental rotational constants and calculated vibration–rotation interaction constants

Pawłowski, Filip; Jørgensen, Poul; Olsen, Jeppe; Hegelund, Flemming; Helgaker, Trygve; Gauss, Ju¨rgen; Bak, Keld L.; Stanton, John F.
April 2002
Journal of Chemical Physics;4/15/2002, Vol. 116 Issue 15, p6482
Academic Journal
A detailed study is carried out of the accuracy of molecular equilibrium geometries obtained from least-squares fits involving experimental rotational constants B[sub 0] and sums of ab initio vibration–rotation interaction constants α[sub r][sup B]. The vibration–rotation interaction constants have been calculated for 18 single-configuration dominated molecules containing hydrogen and first-row atoms at various standard levels of ab initio theory. Comparisons with the experimental data and tests for the internal consistency of the calculations show that the equilibrium structures generated using Hartree–Fock vibration–rotation interaction constants have an accuracy similar to that obtained by a direct minimization of the CCSD(T) energy. The most accurate vibration–rotation interaction constants are those calculated at the CCSD(T)/cc-pVQZ level. The equilibrium bond distances determined from these interaction constants have relative errors of 0.02%–0.06%, surpassing the accuracy obtainable either by purely experimental techniques (except for the smallest systems such as diatomics) or by ab initio methods. © 2002 American Institute of Physics.


Related Articles

  • Commentary on rotations in 3-space. Sullivan, Donald // UMAP Journal;Spring94, Vol. 15 Issue 1, p43 

    Presents solutions to two basic problems concerning rotations in three-dimensional Euclidean space. Determining the axis and angle of rotation; Example.

  • Basics of rotary optical encoders. Orlosky, Scott; Avolio, Glenn // Control Engineering;Nov97, Vol. 44 Issue 15, p75 

    Presents a primer on specifying rotary optical encoders. Relative advantages of different encoder types; Electrical interfaces; Enhancing resolution; Mechanical issues; Factor in the environment.

  • The four final rotation states of Venus. Correia, Alexandre C.M.; Laskar, Jacques // Nature;6/14/2001, Vol. 411 Issue 6839, p767 

    Presents a study that investigates the four final rotation states of the planet Venus. Conservative equations for precessional motion; Mathematical model used for calculating gravitational tides; Overview of the study.

  • Separation of variables for the Rarita–Schwinger equation on all type D vacuum backgrounds. Kamran, N. // Journal of Mathematical Physics;Jul85, Vol. 26 Issue 7, p1740 

    We present a separable master equation governing Rarita-Schwinger spin-3/2 fields, valid in the whole class of type D vacuum backgrounds.

  • On the nature of rotational shear stabilization in toroidal geometry and its numerical... Miller, R.L.; Waltz, R.E. // Physics of Plasmas;Sep94, Vol. 1 Issue 9, p2835 

    Discusses the nature of rotational shear stabilization in toroidal geometry and its numerical representation. Formulation of a one-dimensional model problem in a ballooning mode angle space; Discrete solution; Differences between the analytic continuum eigenmodes and the discrete eigenmodes mode.l.

  • A New Class of Exact Solutions of Euler Equations. Pukhnachov, V. V. // Doklady Physics;Feb2002, Vol. 47 Issue 2, p168 

    Discusses rotationally symmetric motions of an ideal fluid in the absence of external bulk forces. Euler equations admitting a broad transformation group that yields exact solutions to them; Invariant solutions of the Euler equations primarily studied; Analysis of partially invariant solutions...

  • Spinning twirling twisting curling coiling looping wrapping winding SPIRALS. Churchman, Deborah // Ranger Rick;Aug2000, Vol. 34 Issue 8, p34 

    Describes and identifies twisting and curling shapes in nature.

  • Testing Mach's principle in electrodynamics. Fukai, J.; Assis, A. K. T. // Canadian Journal of Physics;Nov2003, Vol. 81 Issue 11, p1239 

    We analyze the consequences of Mach's principle as applied to electromagnetism. This view reveals new effects not predicted by standard electromagnetic theory.PACS Nos.: 41.20.�q, 41.20.Gz

  • Spin structure of antiferromagnetic disclination. Ivanov, B.A.; Kireev, V.E.; Voronov, V.P. // Low Temperature Physics;Aug97, Vol. 23 Issue 8, p635 

    Analyzes the spin structure of magnetic disclination carried out on the basis of discrete model as well as in the specially constructed generalized continual theory based on the local introduction of the antiferromagnetism vector. Disappearance of the modulus of the antiferromagnetism vector at...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics