Intrinsic Distortion Path in the analysis of the Jahn–Teller effect

Zlatar, Matija; Gruden, Maja; Schläpfer, C. W.; Daul, Claude

doi:10.1016/j.theochem.2010.04.020

Cited by 28 publications

(37 citation statements)

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“…The reaction path starting from the high-symmetry geometry G HS to the low-symmetry minimum G M is defined as the intrinsic distortion path (IDP) [23]. In the IDP method, each point X in the APES can be represented as a 3N -dimentional vector R X , and the energy minimum point M is taken as the origin point [ R(G M ) = 0].…”

Section: Intrinsic Distortion Pathmentioning

confidence: 99%

“…However, in the real case there may be many modes coupling to the distortion [22]. To better understand the multimode problem in Jahn-Teller systems, an intrinsic distortion path (IDP) method has been introduced to provide a detailed description of Jahn-Teller distortion and to analyze the role of vibrational modes in the distortion [23]. In the IDP method, the JT distortion is regarded as a superposition of all possible JT active normal modes.…”

Section: Introductionmentioning

confidence: 99%

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Multimode Jahn-Teller effect in bulk systems: A case of the NV0 center in diamond

et al. 2018

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The multimode Jahn-Teller ( JT) effect in a bulk system of a neutral nitrogen-vacancy ( N V 0 ) center in diamond is investigated via first-principles density-functional-theory calculations and the intrinsic distortion path (IDP) method. The adiabatic potential energy surface of the electronic ground state of the N V 0 center is calculated based on the local spin-density approximation. Our calculations confirm the presence of the dynamic Jahn-Teller effect in the ground 2 E state of the N V 0 center. Within the harmonic approximation, the IDP method provides the reactive path of JT distortion from unstable high-symmetry geometry to stable low-symmetry energy minimum geometry, and it describes the active normal modes participating in the distortion. We find that there is more than one vibrational mode contributing to the distortion, and their contributions change along the IDP. Several vibrational modes with large contributions to JT distortion, especially those modes close to 44 meV, are clearly observed as the phonon sideband in photoluminescence spectra in a series of experiments, indicating that the dynamic Jahn-Teller effect plays an important role in the optical transition of the N V 0 center. The multimode Jahn-Teller (JT) effect in a bulk system of a neutral nitrogen-vacancy (NV 0 ) center in diamond is investigated via first-principles density-functional-theory calculations and the intrinsic distortion path (IDP) method. The adiabatic potential energy surface of the electronic ground state of the NV 0 center is calculated based on the local spin-density approximation. Our calculations confirm the presence of the dynamic Jahn-Teller effect in the ground 2 E state of the NV 0 center. Within the harmonic approximation, the IDP method provides the reactive path of JT distortion from unstable high-symmetry geometry to stable low-symmetry energy minimum geometry, and it describes the active normal modes participating in the distortion. We find that there is more than one vibrational mode contributing to the distortion, and their contributions change along the IDP. Several vibrational modes with large contributions to JT distortion, especially those modes close to 44 meV, are clearly observed as the phonon sideband in photoluminescence spectra in a series of experiments, indicating that the dynamic Jahn-Teller effect plays an important role in the optical transition of the NV 0 center. Disciplines Condensed Matter Physics

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Section: Intrinsic Distortion Pathmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Multimode Jahn-Teller effect in bulk systems: A case of the NV0 center in diamond

et al. 2018

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“…Details can be found in our previous papers [5,13,14,15]. The considered molecules have a doubly degenerate electronic ground state, which is coupled with vibrations of a doubly degenerate irreducible representation in the HS point group, thus they belong to the E e JT systems.…”

Section: Resultsmentioning

confidence: 99%

“…and ring-tilt (9% to the R JT ; 55% to the E JT ); a 1 ' is metal-ring stretch (10% to the R JT ; 12% to the E JT ) [5,13,15].…”

Section: Resultsmentioning

confidence: 99%

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Density Functional Theory for the Study of the Multimode Jahn-Teller Effect

Zlatar

Gruden²,

Schläpfer³

et al. 2010

Chimia

Self Cite

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The Jahn-Teller (JT) theorem states that in a molecule with a degenerate electronic state, a structural distortion must occur that lowers the symmetry, removes the degeneracy and lowers the energy. The multideterminental-DFT method performed to calculate the JT parameters for the JT active molecules is described. Within the harmonic approximation the JT distortion can be analyzed as a linear combination of all totally symmetric normal modes in any of the low symmetry minimum energy conformation, which allows calculating the Intrinsic Distortion Path (IDP), exactly from the high symmetry point to the low symmetry configuration. Results obtained by the approach described here give direct insight into the coupling of electronic structure and nuclear movements.

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Threshold Ionization of Cobaltocene: The Metallocene Molecule Revealing Zero Kinetic Energy States

Ketkov

Selzle

2012

Angewandte Chemie

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Dedicated to Professor Gleb Abakumov on the occasion of his 75th birthdaySince the discovery of ferrocene 60 years ago, [1] metallocenes have represented one of the most intriguing classes of organometallics. Numerous theoretical and experimental investigations of electronic structures of these prototypical systems form a basis for understanding the nature and fundamental properties of the metal-ligand delocalized chemical bonds. In contrast, intense chemical interest has been focused on these compounds during the last decade because of their relevance to organic synthesis, catalysis, bioorganometallic chemistry, and materials science. [2] Redox parameters appear to play a key role in tuning the chemical reactivity of cyclopentadienyl metal complexes and properties of the metallocene-based materials. [3] Precise information on ionization energies (IEs) of these sandwich compounds is, therefore, of fundamental importance in predicting their chemical behavior.High-resolution IEs can be obtained with zero kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) techniques [4] based on the laser excitation of jetcooled molecules to high Rydberg levels (ZEKE states) and subsequent ionization by an electric pulse. Recently, fascinating insight into the electronic structures of transition-metal bis(arene) derivatives has been provided by ZEKE and MATI studies. [5] However, no successful attempts to measure the ZEKE or MATI spectra of metallocenes have been reported so far. Multiphoton excitation of [Cp 2 Fe] and [Cp 2 Ni] (Cp = h 5 -cyclopentadienyl) gave no MATI signals, probably because of the instability of the corresponding ZEKE states. [5b] Herein we report the first example of a metallocene MATI spectrum. In this work, we studied cobaltocene which, like ferrocene, represents one of the key sandwich compounds. This complex attracts the attention of theoretical chemists [6] because of its degenerate ground electronic state, 2 E 1 '' in the D 5h point group (the [Cp 2 Co] 19electron configuration is …[3d(e 2 ')] 2 [3d(a 1 ')] 2 [3d(e 1 '')] 1 ). The neutral molecule should, therefore, appropriately lower its symmetry as a result of the Jahn-Teller (JT) effect. This makes it especially interesting to obtain a high-resolution photoionization spectrum of cobaltocene. Moreover, ionization of the [Cp 2 Co] molecule yields the 18-electron cation which is an isoelectronic analogue of the highly symmetric (D 5h ) ferrocene. The surprisingly well-resolved MATI spectrum of [Cp 2 Co] measured in this work demonstrates that the powerful MATI and ZEKE techniques can be efficiently used to investigate fine electronic effects in metallocene molecules.Indeed, when conditions for the one-photon excitation of the cobaltocene ZEKE states in a supersonic jet were found in our experiments, the MATI spectrum having a rich vibronic structure was recorded (Figure 1). In contrast to the classical UV photoelectron spectrum [7] (PES) showing a single broad 3d(e 1 '') ionization band with the full width at half-maximum (FWHM) of...

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Intrinsic Distortion Path in the analysis of the Jahn–Teller effect

Cited by 28 publications

References 28 publications

Multimode Jahn-Teller effect in bulk systems: A case of the NV0 center in diamond

Multimode Jahn-Teller effect in bulk systems: A case of the NV0 center in diamond

Density Functional Theory for the Study of the Multimode Jahn-Teller Effect

Threshold Ionization of Cobaltocene: The Metallocene Molecule Revealing Zero Kinetic Energy States

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