Charge resonance structure of aniline dimer cation

Roy, Madhusudan; Kim, Kuk Ki; Nam, Sang Hwan; Alauddin, M.; Song, Jae Kyu; Park, Seung Min

doi:10.1016/j.ijms.2016.03.007

Cited by 2 publications

(3 citation statements)

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“…Just like in inorganic semiconductors, organic semiconductors exhibit increased conductance by doping with a small fraction of ionized molecules (i.e., holes). In these materials, the radical cation can form a dimer with a neutral molecule to delocalize the positive charge, and it is this monocation dimer that causes a significant increase in the charge mobility in the material. − To explore the use of NOCI-MP2 for aromatic dimer cations, we looked at the binding energy and the charge resonance energy for four examples (aniline, naphthalene, anthracene, and phenalenyl) and compared to gas phase experimental data where available. − Using the ALMO strategy for these species suggests that two diabatic configurations are natural: Monomer +• –Monomer and Monomer–Monomer +• . These will give rise to two NOCI determinants associated with constructive and destructive interference between these localized charge diabatic determinants.…”

Section: Results and Discussionmentioning

confidence: 99%

“… a Experimental data are provided when available. The binding energy is in kcal/mol and the charge resonance energy is in eV. b Values taken from ref . c Values taken from ref . d Values taken from ref . …”

Section: Results and Discussionmentioning

confidence: 99%

“…[90][91][92] To explore the use of NOCI-MP2 for aromatic dimer cations, we looked at the binding energy and the charge resonance energy for 4 examples (aniline, naphthalene, anthracene, and phenalenyl), and compare to gas phase experimental data where available. [93][94][95] Using the ALMO strategy for these species suggests that two diabatic configurations are natural: (Monomer +• -Monomer and Monomer-Monomer +• . These will give rise to two NOCI states associated with constructive and destructive interference between these localized charge diabatic determinants.…”

Section: Charged Dimersmentioning

confidence: 99%

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Efficient Implementation of NOCI-MP2 Using the Resolution of the Identity Approximation with Application to Charged Dimers and Long C–C Bonds in Ethane Derivatives

Yost

Head‐Gordon

2018

J. Chem. Theory Comput.

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An efficient implementation of the perturb-then-diagonalize nonorthogonal configuration interaction method with second-order Møller-Plesset perturbation theory (NOCI-MP2) is presented. Relative to other low scaling multireference perturbation theories, NOCI-MP2 often requires a much smaller active space because of the use of nonorthogonal reference configurations. Reworking the NOCI-MP2 equations with the resolution of the identity (RI) approximation enables the method to have the same memory requirements and computational scaling as single reference RI-MP2. The working equations are extended to include single substitutions as required when the reference determinants do not satisfy the Hartree-Fock equations. A detailed computational algorithm is presented along with timings to establish the performance of the implementation. NOCI-MP2 is applied to the binding energy and charge resonance energy in dication and monocation π dimers, as well as didiamantane ethane, and hexaphenylethane. A well-defined set of nonorthogonal determinants are obtained using absolutely localized molecular orbitals (ALMOs), as solutions to the self-consistent field for molecular interactions (SCF-MI) equations corresponding to covalent and ionic determinants. Agreement with experimental information where available, and other multireference methods, is satisfactory, with the use of an 0.3 au level shift to guard against large MP2 amplitudes. For didiamantane ethane and hexaphenylethane, large dispersion forces help stabilize the molecules despite the steric repulsion. By contrast, in the case of hexaphenylethane, the energy penalty from the geometric distortion of the fragments significantly weakens the bond.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: Charged Dimersmentioning

confidence: 99%

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Efficient Implementation of NOCI-MP2 Using the Resolution of the Identity Approximation with Application to Charged Dimers and Long C–C Bonds in Ethane Derivatives

Yost

Head‐Gordon

2018

J. Chem. Theory Comput.

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Structure of Mono‐Hydrated Aniline Dimer Cation

Alauddin

Roy

Nam

et al. 2020

Bulletin Korean Chem Soc

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Photodissociation spectroscopy of mono-hydrated aniline dimer (An 2 W +) cation was performed to determine its most stable structure and the charge resonance (CR) interaction therein. In its photodissociation action spectrum, two local excitation (LE) bands at $1.9 eV (656 nm) and >3.0 eV (<420 nm), previously assigned to A 2Ã 2 X 2B 1 and B 2B 1 X 2B 1 transition, respectively, for aniline dimer (An 2 +), were also observed for An 2 W +. On the other hand, the absorption band at $1.12 eV (1110 nm) from the CR interaction reported for An 2 + disappeared in case of An 2 W +. Based on this infrared photodissociation action spectra supported by quantum chemical calculations, we suggest that the most stable structure of An 2 W + maintains the stacked structure of An 2 + but H 2 O molecule connected to the amino group of aniline molecule via hydrogen bonding plays a role to suppress the CR interaction.

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Charge resonance structure of aniline dimer cation

Cited by 2 publications

References 50 publications

Efficient Implementation of NOCI-MP2 Using the Resolution of the Identity Approximation with Application to Charged Dimers and Long C–C Bonds in Ethane Derivatives

Efficient Implementation of NOCI-MP2 Using the Resolution of the Identity Approximation with Application to Charged Dimers and Long C–C Bonds in Ethane Derivatives

Structure of Mono‐Hydrated Aniline Dimer Cation

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