The Journal of Chemical Physics

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ISSN / EISSN : 00219606 / 10897690
Current Publisher: AIP Publishing (10.1063)
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Evan Thomas Vickers, Ke Xu, Xueming Li, Jin Zhong Zhang
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5133803

The publisher has not yet granted permission to display this abstract.
Yuzhu Lu, Jing Zhao, Rulin Tang, Xiaoxi Fu, Chuangang Ning
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5134535

Abstract:The latest electron affinity value of an iridium atom is 1.564 36(15) eV, determined via a method based on the Wigner threshold law by Bilodeau and co-workers. However, they observed a significant deviation from the Wigner threshold law in the threshold photodetachment experiment. To address this dilemma, we conducted high-resolution photoelectron spectroscopy of Ir− via the slow-electron velocity-map imaging method in combination with an ion trap. The electron affinity of Ir was measured to be 12 614.97(9) cm−1 or 1.564 057(11) eV. We find that the Wigner threshold law is still valid for the threshold photodetachment of Ir− through a p-wave fitting of the photodetachment channel Ir−5d86s23F4→Ir5d86sb4F9/2. The photoelectron angular distributions of photodetachment channels Ir−5d86s23F4→Ir5d76s2a4F9/2 and Ir−5d86s23F4→Ir5d86sb4F9/2 were also investigated. The behavior of anisotropy parameter β indicates a strong interaction between the two channels. Moreover, the energy level 3P2 of Ir−, which was not observed in the previous works, was experimentally determined to be 4163.24(16) cm−1 above the ground state.The latest electron affinity value of an iridium atom is 1.564 36(15) eV, determined via a method based on the Wigner threshold law by Bilodeau and co-workers. However, they observed a significant deviation from the Wigner threshold law in the threshold photodetachment experiment. To address this dilemma, we conducted high-resolution photoelectron spectroscopy of Ir− via the slow-electron velocity-map imaging method in combination with an ion trap. The electron affinity of Ir was measured to be 12 614.97(9) cm−1 or 1.564 057(11) eV. We find that the Wigner threshold law is still valid for the threshold photodetachment of Ir− through a p-wave fitting of the photodetachment channel Ir−5d86s23F4→Ir5d86sb4F9/2. The photoelectron angular distributions of photodetachment channels Ir−5d86s23F4→Ir5d76s2a4F9/2 and Ir−5d86s23F4→Ir5d86sb4F9/2 were also investigated. The behavior of anisotropy parameter β indicates a strong interaction between the two channels. Moreover, the energy level 3P2 of Ir−, which was not obs...
Ruo Xi Yang, Liang Z. Tan
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5128016

Abstract:Inorganic halide perovskites CsPbX3 (X = Cl, Br, I) have been widely studied as colloidal quantum dots for their excellent optoelectronic properties. Not only is the long-term stability of these materials improved via nanostructuring, their optical bandgaps are also tunable by the nanocrystal (NC) size. However, theoretical understanding of the impact of the NC size on the phase stability and bandgap is still lacking. In this work, the relative phase stability of CsPbI3 as a function of the crystal size and the chemical potential is investigated by density functional theory. The optically active phases (α- and γ-phase) are found to be thermodynamically stabilized against the yellow δ-phase by reducing the size of the NC below 5.6 nm in a CsI-rich environment. We developed a more accurate quantum confinement model to predict the change in bandgaps at the sub–10 nm regime by including a finite-well effect. These predictions have important implications for synthesizing ever more stable perovskite NCs and bandgap engineering.Inorganic halide perovskites CsPbX3 (X = Cl, Br, I) have been widely studied as colloidal quantum dots for their excellent optoelectronic properties. Not only is the long-term stability of these materials improved via nanostructuring, their optical bandgaps are also tunable by the nanocrystal (NC) size. However, theoretical understanding of the impact of the NC size on the phase stability and bandgap is still lacking. In this work, the relative phase stability of CsPbI3 as a function of the crystal size and the chemical potential is investigated by density functional theory. The optically active phases (α- and γ-phase) are found to be thermodynamically stabilized against the yellow δ-phase by reducing the size of the NC below 5.6 nm in a CsI-rich environment. We developed a more accurate quantum confinement model to predict the change in bandgaps at the sub–10 nm regime by including a finite-well effect. These predictions have important implications for synthesizing ever more stable perovskite NCs and ban...
Jian-Chun Wu, Tian-Wen Dong, Gui-Wen Jiang, Meng An, Bao-Quan Ai
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5141040

The publisher has not yet granted permission to display this abstract.
Francesco Avanzini, Gianmaria Falasco, Massimiliano Esposito
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5143654

Peng-Li Du, Yao Wang, Rui-Xue Xu, Hou-Dao Zhang, Yijing Yan
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5134745

Abstract:In this work, we establish a so-called “system–bath entanglement theorem,” for arbitrary systems coupled with Gaussian environments. This theorem connects the entangled system–bath response functions in the total composite space to those of local systems, as long as the interacting bath spectral densities are given. We validate the theorem with direct evaluation via the exact dissipation-equation-of-motion approach. Therefore, this work enables various quantum dissipation theories, which originally describe only the reduced system dynamics, for their evaluations on the system–bath entanglement properties. Numerical demonstrations are carried out on the Fano interference spectroscopies of spin–boson systems.In this work, we establish a so-called “system–bath entanglement theorem,” for arbitrary systems coupled with Gaussian environments. This theorem connects the entangled system–bath response functions in the total composite space to those of local systems, as long as the interacting bath spectral densities are given. We validate the theorem with direct evaluation via the exact dissipation-equation-of-motion approach. Therefore, this work enables various quantum dissipation theories, which originally describe only the reduced system dynamics, for their evaluations on the system–bath entanglement properties. Numerical demonstrations are carried out on the Fano interference spectroscopies of spin–boson systems.
Boris V. Merinov, Saber Naserifar, Sergey V. Zybin, Sergey Morozov, William A. Goddard, Jinuk Lee, Jae Hyun Lee, Hyea Eun Han, Young Cheol Choi, Seung Ha Kim
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5132566

Abstract:We previously reported comprehensive density functional theory-molecular dynamics (DFT-MD) at 400 K to determine the composition and structure of the solid electrolyte interface (SEI) between a Li anode and [Pyr14][TFSI] ionic liquid. In this paper, we examined diffusion rates in both the Li-electrode region and SEI compact layer in smaller 83Li/2[TFSI] and larger 164Li/4[TFSI] systems. At 400 K, the Li-diffusion constant in the Li-region is 1.35 × 10−10 m2/s for 83Li/2[TFSI] and 5.64 × 10−10 m2/s for 164Li/4[TFSI], while for the SEI it is 0.33 × 10−10 m2/s and 0.22 × 10−10 m2/s, thus about one order slower in the SEI compared to the Li-region. This Li-diffusion is dominated by hopping from the neighbor shell of one F or O to the neighbor shell of another. Comparing the Li-diffusion at different temperatures, we find that the activation energy is 0.03 and 0.11 eV for the Li-region in the smaller and larger systems, respectively, while for the SEI it is 0.09 and 0.06 eV.We previously reported comprehensive density functional theory-molecular dynamics (DFT-MD) at 400 K to determine the composition and structure of the solid electrolyte interface (SEI) between a Li anode and [Pyr14][TFSI] ionic liquid. In this paper, we examined diffusion rates in both the Li-electrode region and SEI compact layer in smaller 83Li/2[TFSI] and larger 164Li/4[TFSI] systems. At 400 K, the Li-diffusion constant in the Li-region is 1.35 × 10−10 m2/s for 83Li/2[TFSI] and 5.64 × 10−10 m2/s for 164Li/4[TFSI], while for the SEI it is 0.33 × 10−10 m2/s and 0.22 × 10−10 m2/s, thus about one order slower in the SEI compared to the Li-region. This Li-diffusion is dominated by hopping from the neighbor shell of one F or O to the neighbor shell of another. Comparing the Li-diffusion at different temperatures, we find that the activation energy is 0.03 and 0.11 eV for the Li-region in the smaller and larger systems, respectively, while for the SEI it is 0.09 and 0.06 eV.
Dongwoo Kim, Hojoon Lim, Sung Soo Ha, Okkyun Seo, Sung Su Lee, Jinwoo Kim, Ki-Jeong Kim, Lucia Perez Ramirez, Jean-Jacques Gallet, Fabrice Bournel, et al.
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5134653

Abstract:The correlation between the structural phase transition (SPT) and oxygen vacancy in SrRuO3 (SRO) thin films was investigated by in situ X-ray diffraction (XRD) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In situ XRD shows that the SPT occurs from a monoclinic SRO phase to a tetragonal SRO phase near ∼200 °C, regardless of the pressure environment. On the other hand, significant core level shifts in both the Ru and Sr photoemission spectra are found under ultrahigh vacuum, but not under the oxygen pressure environment. The directions and behavior of the core level shift of Ru and Sr are attributed to the formation of oxygen vacancy across the SPT temperature of SRO. The analysis of in situ XRD and AP-XPS results provides an evidence for the formation of metastable surface oxide possibly due to the migration of internal oxygen atoms across the SPT temperature, indicating the close relationship between oxygen vacancy and SPT in SRO thin films.The correlation between the structural phase transition (SPT) and oxygen vacancy in SrRuO3 (SRO) thin films was investigated by in situ X-ray diffraction (XRD) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). In situ XRD shows that the SPT occurs from a monoclinic SRO phase to a tetragonal SRO phase near ∼200 °C, regardless of the pressure environment. On the other hand, significant core level shifts in both the Ru and Sr photoemission spectra are found under ultrahigh vacuum, but not under the oxygen pressure environment. The directions and behavior of the core level shift of Ru and Sr are attributed to the formation of oxygen vacancy across the SPT temperature of SRO. The analysis of in situ XRD and AP-XPS results provides an evidence for the formation of metastable surface oxide possibly due to the migration of internal oxygen atoms across the SPT temperature, indicating the close relationship between oxygen vacancy and SPT in SRO thin films.
Nikita N. Lukzen, Konstantin L. Ivanov, Vladimir M. Sadovsky, Renad Z. Sagdeev
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5131583

The publisher has not yet granted permission to display this abstract.
Helen O. Leung, Mark D. Marshall
Published: 21 January 2020
The Journal of Chemical Physics, Volume 152; doi:10.1063/1.5141073

Abstract:The microwave rotational spectrum of the gas-phase bimolecular heterodimer formed between cis-1,2-difluoroethylene and acetylene is obtained using Fourier transform microwave spectroscopy from 5.9 to 21.2 GHz. Rotational constants derived from the analysis of the spectra for the normal isotopologue and singly substituted 13C isotopologues, obtained in natural abundance, allow the determination of the structure of the complex, which, in the absence of a fluorine-hydrogen atom pair located cis to each other, adopts a sterically disfavored geometry (“side-binding”) in which the acetylene interacts with a geminal fluorine-hydrogen atom pair. Structural details are found to be similar to those of previously studied heterodimers with side-binding of acetylene to fluorine while reflecting the degree of halosubstitution. A detailed comparison with the (Z)-1-chloro-2-fluoroethylene-acetylene complex reveals information regarding the relaxed steric requirements for hydrogen bonding to chlorine as opposed to hydrogen bonding to fluorine.The microwave rotational spectrum of the gas-phase bimolecular heterodimer formed between cis-1,2-difluoroethylene and acetylene is obtained using Fourier transform microwave spectroscopy from 5.9 to 21.2 GHz. Rotational constants derived from the analysis of the spectra for the normal isotopologue and singly substituted 13C isotopologues, obtained in natural abundance, allow the determination of the structure of the complex, which, in the absence of a fluorine-hydrogen atom pair located cis to each other, adopts a sterically disfavored geometry (“side-binding”) in which the acetylene interacts with a geminal fluorine-hydrogen atom pair. Structural details are found to be similar to those of previously studied heterodimers with side-binding of acetylene to fluorine while reflecting the degree of halosubstitution. A detailed comparison with the (Z)-1-chloro-2-fluoroethylene-acetylene complex reveals information regarding the relaxed steric requirements for hydrogen bonding to chlorine as opposed to hydroge...