Comments on H/D Isotope Effects on Polarizabilities of Small Molecules. Correlation with Virial Coefficient, Molar Volume, and Electronic Second Moment Isotope Effects

Hook, W. Alexander Van; Wolfsberg, Max

doi:10.1515/zna-1994-4-508

Cited by 9 publications

(5 citation statements)

References 19 publications

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“…We also compared the effect of OH and CH deuteration on the observed shift under strong coupling (red squares on Figure ). Deuteration not only lowers the vibrational energy but also introduces subtle modifications to the molecular geometry and polarity. − …”

Section: Resultsmentioning

confidence: 99%

Solvent Polarity under Vibrational Strong Coupling

Piejko,

Patrahau,

Joseph

et al. 2023

J. Am. Chem. Soc.

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Vibrational strong coupling (VSC) occurs when molecular vibrations hybridize with the modes of an optical cavity, an interaction mediated by vacuum fluctuations. VSC has been shown to influence the rates and selectivity of chemical reactions. However, a clear understanding of the mechanism at play remains elusive. Here, we show that VSC affects the polarity of solvents, which is a parameter well-known to influence reactivity. The strong solvatochromic response of Reichardt’s dye (RD) was used to quantify the polarity of a series of alcohol solvents at visible wavelengths. We observed that, by simultaneously coupling the OH and CH vibrational bands of the alcohols, the absorption maximum of Reichardt’s dye redshifted by up to ∼15.1 nm, corresponding to an energy change of 5.1 kJ·mol–1. With aliphatic alcohols, the magnitude of the absorption change of RD was observed to be related to the length of the alkyl chain, the molecular surface area, and the polarizability, indicating that dispersion forces are impacted by strong coupling. Therefore, we propose that dispersion interactions, which themselves originate from vacuum fluctuations, are impacted under strong coupling and are therefore critical to understanding how VSC influences chemistry.

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Section: Resultsmentioning

confidence: 99%

Solvent Polarity under Vibrational Strong Coupling

Piejko,

Patrahau,

Joseph

et al. 2023

J. Am. Chem. Soc.

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“…Next, we examine the contribution to stabilization of the crystal structure originating from the interaction between instantaneous dipole changes. This contribution is closely related to the dispersion energy and is related to polarizability associated with the nuclear motion of quantum H and D. 29,30 As mentioned earlier, the FT-DACF results suggest that the intensity for IR absorption in deuterated P3HT (and hence also the polarizability) is reduced compared to that of the protonated case. The polarizability is associated with the induction and dispersion forces between molecules.…”

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 61%

Deuteration as a Means to Tune Crystallinity of Conducting Polymers

Jakowski

Huang

Garashchuk

et al. 2017

J. Phys. Chem. Lett.

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The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of the dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton-proton and deuteron-deuteron motions but not of the proton-deuteron motion. Thus, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.

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“…(6,8,9) The numerator is thus proportional to the closure-averaged, squared electronic transition moment; the parameter n¯( is the corresponding closure-averaged frequency equivalent for the state-to-state energy (conveniently expressed in wavenumbers, that is n¯in cm −1 , or elsewhere in nm −1 as convenient), and is called the dispersion parameter (since it describes the frequency dependence of RI), and a 0 is the static polarizability. Now consider, in difference formalism, a more nearly complete expression for the concentration dependence of equation (9):…”

Section: Second-stage Correlation; the Dispersion Correctionmentioning

confidence: 99%

“…(9) R i,n = {(n 2 − 1)/(n 2 + 2)} n V°m ,i = N A a(n)/(3o 0 Equation (1) defines the molar refraction, R i,n . V°m ,i is the standard state molar volume, N A is Avogadro's number, and a(n) is the frequency-dependent polarizability.…”

Section: Introductionmentioning

confidence: 99%