Dynamical Jahn-Teller Effect in Hydrocarbon Radicals

Hobey, William D.; McLachlan, Anton

doi:10.1063/1.1731485

Cited by 199 publications

(61 citation statements)

References 26 publications

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“…Theoretical works trace back to Andy Liehr in 1956 [54]. They span many different methods [5,12,17,26,43,45,50,54,59,72,85] during the years. The values of E JT obtained are summarised in Table 3.…”

Section: Cyclopentadienyl Radicalmentioning

confidence: 99%

“…The various other theoretical methods give different results ranging from 495 to 5,072 cm 1 . Studies of Miller et al [5,6] who used complete active space methods (E JT D 2147cm 1 ) and dispersed fluorescence spectroscopy (E JT D 1237cm 1 ), as well as fitting of ab initio calculations to the spectra [72] 728 Semiempirical-MO [43] 495 HF/STO-3G [59] 5,072 CI/STO-3G [17] 2,484 HF/6-311+G* [26] 1,452 MP2/6-311+G* [26] 3,065 MP4/6-311+G* [26] 2,581 CCSD/6-311+G* [26] 1,613 CCSD(T)/6-311+G* [26] 1,613 CASSCF/cc-PVDZ [12] 2,139 CASSCF/6-31G* [5] 2,147/1,463 CASSCF/cc-PVDZ [50] 1,665 CISD/cc-PVDZ [85] 2,553 EOMIP-CCSD/DZP [45] 1,581 DFT(LDA)/TZP (E JT D 1;463cm 1 ) are considered to be benchmark results for the determination of the JT parameters. They also identified three dominant normal modes necessary to explain their results.…”

Section: Cyclopentadienyl Radicalmentioning

confidence: 99%

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A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Zlatar

Schläpfer

Daul

2009

Springer Series in Chemical Physics

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A new method for the analysis of the adiabatic potential energy surfaces of Jahn-Teller (JT) active molecules is presented. It is based on the analogy between the JT distortion and reaction coordinates. Within the harmonic approximation the JT distortion can be analysed as the linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Contribution of the normal modes to the distortion, their energy contribution to the JT stabilisation energy, the forces at high symmetry cusp and detailed distortion path can be estimated quantitatively. This approach gives direct insight into the coupling of electronic structure and nuclear displacements. Further more, it is reviewed how multideterminental DFT can be applied for the calculation of the JT parameters. As examples the results for VCl 4 , cyclopentadienyl radical and cobaltocene are given.

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Section: Cyclopentadienyl Radicalmentioning

confidence: 99%

Section: Cyclopentadienyl Radicalmentioning

confidence: 99%

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Zlatar

Schläpfer

Daul

2009

Springer Series in Chemical Physics

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“…(For a special two-fold set this was discussed in [286,287].) Computations performed with the diabatic set are much simpler than those with the adiabatic set.…”

Section: The Adiabatic To Diabatic Transformation (Adt)mentioning

confidence: 99%

Complex States of Simple Molecular Systems

Englman¹,

Yahalom²

2002

Advances in Chemical Physics

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A review is given of phase properties in molecular wave functions, composed of a number of (and, at least, two) electronic states that become degenerate at some nearby values of the nuclear configuration. Apart from discussing phases and interference in classical (non-quantal) systems, including light-waves, the review looks at the constructability of complex wave functions from observable quantities ("the phase problem"), at the controversy regarding quantum mechanical phase-operators, at the modes of observability of phase and at the role of phases in some non-demolition measurements. Advances in experimental and (especially) theoretical aspects of Aharonov-Bohm and topological (Berry) phases are described, including those involving two-electron and relativistic systems. Several works in the phase control and revivals of molecular wave-packets are cited as developments and applications of complex-function theory. Further topics that this review touches on are: coherent states, semiclassical approximations and the Maslov index. The interrelation between time and the complex state is noted in the contexts of time delays in scattering, of time-reversal invariance and of the existence of a molecular time-arrow.When the stationary Born-Oppenheimer description for nearly degenerate state is regarded as "embedded" in a broader dynamic formulation, namely through solution of the time dependent Schrödinger equation, the wave function becomes necessarily complex. The analytic behavior of this function in the complex time-plane can be exploited to gain information about the connection between phases and moduli of the componentamplitudes. One form of this connection are a pair of reciprocal (Kramers-Kronig type) relations in the complex time-domain. These show that certain phase changes in a component amplitude (such as, e.g., lead to a non-zero Berry-phase) require changes in the amplitude-moduli, too, and imply degeneracies of the electronic state.The subject of conical degeneracy, or intersection, of adjacent potential surface is extended to nonlinear nuclear-electronic coupling, which can then result in multiple conical degeneracies on a nuclear coordinate plane. We treat cases of double and fourfold intersections, the latter under trigonal symmetry, and employ an analytic-graphical phase tracing method to obtain the resulting Berry phases as the system circles around some or all of the degeneracy points. These phases can take up values that are all integral multiples of π, with integers that vary with the physical situation (or with the model postulated for it).A further type of invariance, with respect to gauge transformation, is also tied to the complex form of the wave function. For a many-component state this leads to a consideration of tensorial (Yang-Mills type) fields F for molecular systems. It is shown that it is the truncation of the Born-Oppenheimer electron-nuclear superposition that generates the molecular Yang-Mills fields.The equations of motion for the nuclear degrees of freedom are derived from a Lagr...

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“…[13][14][15][16][17][18][19][20] This interest originates not only from its relationship to the parent neutral benzene molecule but also from the unique properties which the benzene cation possesses. Neutral benzene has the dominant electronic configuration of…”

Section: Introductionmentioning

confidence: 99%

Calculation of the Jahn-Teller effect in benzene cation: Application to spectral analysis

Applegate

Miller

2002

The Journal of Chemical Physics

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Ab initio calculations have been performed for the cations of benzene, C6H6, and its fluorinated analogues, C6F6 and C6H3F3. Calculated molecular parameters characterizing the Jahn-Teller potential energy surface (PES) are very consistent with those derived from the spectra of C6F However the calculated Jahn-Teller stabilization energy for the benzene cation is roughly three times greater than that previously reported experimentally. With the aid of the calculated values, a more complete analysis of the available spectral data for C6H6+ and C6D6 + is performed, with an emphasis on the data from ZEKE experiments and IR spectra of the Ar·C6H6 + , Ne·C6H6 + , and Ar·C6D6 + complexes.The comprehensive analysis reveals Jahn-Teller activity in 3 e2g modes for C6(H/D)

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Dynamical Jahn-Teller Effect in Hydrocarbon Radicals

Cited by 199 publications

References 26 publications

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Complex States of Simple Molecular Systems

Calculation of the Jahn-Teller effect in benzene cation: Application to spectral analysis

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