Quantum Mechanical Study of Optical Emission Spectra of Rydberg-Excited<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi>H</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>and Its Isotopomers

Mahapatra, S.; Köppel, Horst

doi:10.1103/physrevlett.81.3116

Cited by 44 publications

(32 citation statements)

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“…The JT effect in the C 2 E electronic manifold is also quite weak when compared to the similar other examples treated in the literature. [29][30][31] To this end we note that besides the model study presented here, which, in fact, reproduces the experimental results reasonably well, a more rigorous electronic structure calculations to establish the anionic and neutral potential energy surfaces and the nonadiabatic coupling elements are presently being carried out with an aim to perform wave packet dynamical simulations to study the decay of the excited electronic states of B 3 cluster.…”

Section: Discussionmentioning

confidence: 61%

“…The JT coupling within the C 2 E electronic manifold is also weak compared to similar strong (E ⊗ e)-JT coupling cases treated in the literature. [29][30][31] To this end we mention that photodetachment experiments for the smallest boron clusters are reported to be quite delicate because of weak cluster intensities and low photodetachment cross sections. 15 The resolution of the apparatus was ∼30 meV for 1 eV electrons.…”

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confidence: 98%

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The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster

2006

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The photodetachment spectroscopy of B3- anion is theoretically studied with the aid of a quantum dynamical approach. The theoretical results are compared with the available experimental photoelectron spectra of B3-. Both B3- and B3 possess D(3h) symmetry at the equilibrium configuration of their electronic ground state. Distortion of B3 along its degenerate vibrational mode nu2 splits the degeneracy of its excited C2E' electronic manifold and exhibits (E [symbol: see text] e)-Jahn-Teller (JT) activity. The components of the JT split potential energy surface form conical intersections, and they can also undergo pseudo-Jahn-Teller (PJT) crossings with the X2A1' electronic ground state of B3 via the degenerate nu2 vibrational mode. The impact of the JT and PJT interactions on the nuclear dynamics of B3 in its X2A1'-C2E' electronic states is examined here by establishing a diabatic model Hamiltonian. The parameters of the electronic part of this Hamiltonian are calculated by performing electronic structure calculations and the nuclear dynamics on it is simulated by solving quantum eigenvalue equation. The theoretical results are in good accord with the experimental data.

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Section: Discussionmentioning

confidence: 61%

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confidence: 98%

The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster

2006

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“…According to the symmetry rule the b 1 and b 2 modes cannot be active in first-order in the e X state, however, they are so in the e A state and can split the electronic degeneracy. The situation here is different from the extensively studied (E e)-JT effect (in which electronic degeneracy is split by degenerate e vibrational mode) in the literature [5,6,14,[18][19][20][21]. In the present case the splitting of the degeneracy of the E state is caused by the JT active nondegenerate b 1 and b 2 vibrational modes, known as the (E b)-JT effect [6,14].…”

Section: Introductionmentioning

confidence: 65%

“…The latter simulation is necessary to infer and assign the dominant progressions observed in the experiment. In the full e X-e A coupled state dynamical simulation performed here, we retained four a 1 (m 1 -m 4 ), two b 1 (m 6 -m 7 ), three b 2 (m 10 , m 11 and m 13 ) and four e (m 16 -m 19 ) vibrational modes. The number of SPF basis functions allocated to a given mode is estimated depending on its coupling strength and the convergence of the spectral envelope.…”

Section: Vibronic Spectrummentioning

confidence: 99%

(B+E⊗b)⊗e Jahn–Teller and pseudo-Jahn–Teller effects in the spiropentane radical cation

2010

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“…7,11,[25][26][27][28][29][30] The e modes cease to be JT active in tetragonal systems. In this case, the JT perturbation of an E state is caused by the nondegenerate vibrational modes of b symmetry, known as (EXb)-JT effect.…”

Section: The Jahn-teller and Pseudojahn-teller Interactionsmentioning

confidence: 99%

Excited Electronic States and Nonadiabatic Effects in Contemporary Chemical Dynamics

Mahapatra

2009

Acc. Chem. Res.

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The question of how to describe the crossing of molecular electronic states is one of the most challenging issues in contemporary chemical dynamics. In recent years, the fundamental concept of conical intersections (CIs) of electronic potential energy surfaces (PESs) has emerged, which allows extremely fast and efficient switching of a molecule between its excited and ground electronic states. CIs are ubiquitous in polyatomic molecules. Because they generically allow the crossings of the Born-Oppenheimer (BO) adiabatic PESs, they have become the crucial mechanistic elements of the rapidly growing area of nonadiabatic chemistry. The most critical consequence of CIs is a complete breakdown of the adiabatic BO approximation. That means that the reorganization of fast-moving electrons and nuclear vibrations must be treated concurrently. Ideally, the theoretical description should be quantum mechanical in this situation. However, because of the complexity, the necessary approximations often make it difficult to conclusively predict dynamic behavior of large polyatomic molecules. In addition, a nonunique diabatic electronic representation (describing coupling between states in the electronic Hamiltonian) is essential to avoid the singular nature of the nuclear kinetic coupling terms of the unique adiabatic electronic representation. This Account describes both the challenges and some recent advances in quantum mechanical studies of nonadiabatic molecular processes, highlighting results from our recent work examining the static aspects of CIs and their dynamical consequences. The spectroscopic implications of the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) intersections in complex molecular systems are discussed. Our work probes the underlying details of complex vibronic spectra of systems of growing sizes in terms of both electronic and nuclear degrees of freedom. The necessity of extension of the theoretical treatment beyond a linear vibronic coupling approach is addressed. Our results establish highly overlapping band structures due to JT and PJT CIs, a bimodal distribution of spectral intensity that originates from strong JT coupling, and the role of intermode bilinear coupling in the progressions of vibronic bands. Investigations of the quantum dynamics of the prototypical naphthalene radical cation were aimed at understanding its photostability, lack of fluorescence emissions, and diffuse interstellar bands. This work established extremely fast relaxation of this radical cation through CIs. Simulations of the interplay of electronic and relativistic spin-orbit coupling in the photodetachment spectroscopy of ClH(2)(-), in conjunction with experimental data, support the existence of a shallow van der Waals well in the reactive Cl + H(2) PES. These results also reveal a quenching of electronic coupling by the relatively strong spin-orbit coupling. In addition, we studied the dynamics of the prototypical H + H(2) reaction from a new perspective by explicitly including the coupling between the two energy surfaces of ...

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Quantum Mechanical Study of Optical Emission Spectra of Rydberg-ExcitedH3and Its Isotopomers

Cited by 44 publications

References 29 publications

The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster

The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster

(B+E⊗b)⊗e Jahn–Teller and pseudo-Jahn–Teller effects in the spiropentane radical cation

Excited Electronic States and Nonadiabatic Effects in Contemporary Chemical Dynamics

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Quantum Mechanical Study of Optical Emission Spectra of Rydberg-ExcitedH3and Its Isotopomers

Cited by 44 publications

References 29 publications

The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B3 cluster

The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B3 cluster

(B+E⊗b)⊗e Jahn–Teller and pseudo-Jahn–Teller effects in the spiropentane radical cation

Excited Electronic States and Nonadiabatic Effects in Contemporary Chemical Dynamics

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The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster

The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster