Infrared Signatures of a Water Molecule Attached to Triatomic Domains of Molecular Anions:  Evolution of the H-bonding Configuration with Domain Length

Robertson, William H.; Price, Erica A.; Weber, J. Mathias; Shin, Jae–Heon; Weddle, Gary H.; Johnson, Mark A.

doi:10.1021/jp030474v

Cited by 78 publications

(135 citation statements)

References 34 publications

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“…NO − 2 ·H 2 O, which would be even smaller, has been discarded since its C 2v structure is not the lowest energy structure. 23 HCO − 2 ·H 2 O exhibits the same Franck-Condon-like progression as the other clusters in addition to a broad background (see supplementary material of Ref. 26 and Fig.…”

Section: Introductionmentioning

confidence: 75%

“…23 That is, we considered the two OH-stretch modes of the water molecule (q 1 and q 2 , which we define as local modes rather than the symmetric and asymmetric stretch vibrations, see Fig. 1(a)), as well as the HOH bending mode (q 3 ) because of its Fermi-resonance with the OH stretching modes.…”

Section: B Definition Of Inter-and Intramolecular Coordinatesmentioning

confidence: 99%

“…That is, the OH stretch vibration of the water molecule splits into a single pronounced "Franck-Condon"-like progression due to the strong anharmonic coupling to the water rocking mode. 18,22,23 Furthermore, this Franck-Condon progression sits on a broad background that might indicate an ultrafast relaxation channel. While the Franck-Condon progression has been reproduced using cubic ab initio derived force constants, 18,22 the broad background and its underlying dynamics still awaits an explanation.…”

Section: Introductionmentioning

confidence: 98%

“…18,[23][24][25][26] In addition in related work, Neumark and coworkers have studied the complex with NO − 3 . 27 Despite the fact that these complexes show all the nontrivial features of the IR spectroscopy of hydrogen bonds, their spectral signatures are particularly simple.…”

Section: Introductionmentioning

confidence: 99%

“…8(c)), the latter of which, however, being less pronounced as compared to complexes with either CH 3 NO − 2 or CH 3 CO − 2 . 23 Including three intramolecular and three intermolecular degrees of freedom, we explore the coherent (i.e., oscillatory) population transfer after excitation of the OH-stretch vibration into the HOH-bend overtone, which is in close resonance and coupled to the OH-stretch vibration by a conical intersection. Furthermore, relaxation into the HOH-bend fundamental and the ground state is observed, which occurs in an incoherent (i.e., exponential) manner.…”

Section: Introductionmentioning

confidence: 99%

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Nonadiabatic vibrational dynamics in the HCO2−⋅H2O complex

Hamm

Stock

2015

The Journal of Chemical Physics

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Based on extensive ab initio calculations and the time-propagation of the nuclear Schrödinger equation, we study the vibrational relaxation dynamics and resulting spectral signatures of the OH stretch vibration of a hydrogen-bonded complex, HCO − 2 H 2 O. Despite their smallness, it has been shown experimentally by Johnson and coworkers that the gas-phase infrared spectra of these types of complexes exhibit much of the complexity commonly observed for hydrogen-bonded systems. That is, the OH stretch band exhibits a significant red shift together with an extreme broadening and a pronounced substructure, which reflects its very strong anharmonicity. Employing an adiabatic separation of time scales between the three intramolecular high-frequency modes of the water molecule and the three most important intermolecular low-frequency modes of the complex, we calculate potential energy surfaces (PESs) of the ground and the first excited states of the high-frequency modes and identify a vibrational conical intersection between the PESs of the OH stretch fundamental and the HOH bend overtone. By performing a time-dependent propagation of the resulting system, we show that the conical intersection affects a coherent population transfer between the two states, the first step of which being ultrafast (60 fs) and irreversible. The subsequent relaxation of vibrational energy into the HOH bend and ground state occurs incoherently but also quite fast (1 ps), although the corresponding PESs are well separated in energy. Owing to the smaller effective mass difference between light and heavy degrees of freedom, the adiabatic ansatz is consequently less significant for vibrations than in the electronic case. Based on the model, we consider several approximations to calculate the measured Ar-tag action spectrum of HCO − 2 H 2 O and achieve semiquantitative agreement with the experiment. Based on extensive ab initio calculations and the time-propagation of the nuclear Schrödinger equation, we study the vibrational relaxation dynamics and resulting spectral signatures of the OH stretch vibration of a hydrogen-bonded complex, HCO − 2 · H 2 O. Despite their smallness, it has been shown experimentally by Johnson and coworkers that the gas-phase infrared spectra of these types of complexes exhibit much of the complexity commonly observed for hydrogen-bonded systems. That is, the OH stretch band exhibits a significant red shift together with an extreme broadening and a pronounced substructure, which reflects its very strong anharmonicity. Employing an adiabatic separation of time scales between the three intramolecular high-frequency modes of the water molecule and the three most important intermolecular low-frequency modes of the complex, we calculate potential energy surfaces (PESs) of the ground and the first excited states of the high-frequency modes and identify a vibrational conical intersection between the PESs of the OH stretch fundamental and the HOH bend overtone. By performing a time-dependent propagation of the resulti...

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Section: Introductionmentioning

confidence: 75%

Section: B Definition Of Inter-and Intramolecular Coordinatesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Nonadiabatic vibrational dynamics in the HCO2−⋅H2O complex

Hamm

Stock

2015

The Journal of Chemical Physics

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Performance of density‐functional tight‐binding models in describing hydrogen‐bonded anionic‐water clusters

2014

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Density-functional tight-binding (DFTB) models are computationally efficient approximations to density-functional theory that have been shown to predict reliable structural and energetic properties for various systems. In this work, the reliability and accuracy of the self-consistent-charge DFTB model and its recent extension(s) in predicting the structures, binding energies, charge distributions, and vibrational frequencies of small water clusters containing polyatomic anions of the Hofmeister series (carbonate, sulfate, hydrogen phosphate, acetate, nitrate, perchlorate, and thiocyanate) have been carefully and systematically evaluated on the basis of high-level ab initio quantum-chemistry [MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVQZ] reference data. Comparison with available experimental data has also been made for further validation. The self-consistent-charge DFTB model, and even more so its recent extensions, are shown to properly account for the structural properties, energetics, intermolecular polarization, and spectral signature of hydrogen-bonding in anionic water clusters at a fraction of the computational cost of ab initio quantum-chemistry methods. This makes DFTB models candidates of choice for investigating much larger systems such as seeded water droplets, their structural properties, formation thermodynamics, and infrared spectra.

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Effect of microhydration on the atmospherically important metastable carbonyl sulfide anion: Structure, energetic, and infrared study

Mondal

Teja

Singh

2015

Int J of Quantum Chemistry

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Structure, energetics, and vibrational frequency of the microhydrated carbonyl sulfide anion [OCS−(H2O)n (n = 1–6)] have been explored by the systematic ab initio study to have a comprehensive understanding about the hydration‐induced stabilization phenomenon of OCS−. Water binds with the OCS− in single hydrogen‐bonded (SHB) or double hydrogen‐bonded (DHB) fashion with OH ⋯S and OH ⋯O contacts. Maximum five water molecules can stay in a cyclic water network of these hydrated clusters forming interwater hydrogen bonding (IHB) with each other and out of this, maximum of two water molecules can bind directly to the OCS− in (DHB) arrangement. The stabilization energy values of OCS−(H2O)n depict that ion–water interaction is significant up to four water molecules and beyond that OCS− is stabilized by IHB between the water molecules. The CO stretching frequency of OCS− gets red shifted, whereas CS stretching frequency gets blue shifted on hydration. Charge analysis of hydrated clusters of OCS− indicates that negative charge moves toward oxygen from sulfur on hydration. © 2015 Wiley Periodicals, Inc.

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Infrared Signatures of a Water Molecule Attached to Triatomic Domains of Molecular Anions: Evolution of the H-bonding Configuration with Domain Length

Cited by 78 publications

References 34 publications

Nonadiabatic vibrational dynamics in the HCO2−⋅H2O complex

Nonadiabatic vibrational dynamics in the HCO2−⋅H2O complex

Performance of density‐functional tight‐binding models in describing hydrogen‐bonded anionic‐water clusters

Effect of microhydration on the atmospherically important metastable carbonyl sulfide anion: Structure, energetic, and infrared study

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