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Title: Beyond Duality: Rationalizing Repulsive Coulomb Barriers in Host–Guest Cyclodextrin–Dodecaborate Complexes

Journal Article · · Journal of Physical Chemistry Letters
ORCiD logo [1];  [2];  [2];  [3];  [4];  [5];  [2]; ORCiD logo [6]
  1. East China Normal Univ. (ECNU), Shanghai (China); ShanghaiTech Univ. (China)
  2. East China Normal Univ. (ECNU), Shanghai (China)
  3. ShanghaiTech Univ. (China)
  4. Wuhan Univ. (China)
  5. East China Normal Univ. (ECNU), Shanghai (China); Shanxi Univ., Taiyuan (China); New York University Shanghai (China)
  6. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
+ Show Author Affiliations

The repulsive Coulomb barrier (RCB), an intrinsic potential energy barrier along electron detachment or charge-separation coordinates in multiply charged anions (MCAs), provides dynamic stability to MCAs whose electronic and thermodynamic stabilities are largely dictated by strong internal Coulomb repulsions. Spectroscopic and theoretical characterizations of the RCB have been focused on isolated MCAs. In this work, we extend the RCB investigation beyond the previous scope by including noncovalent host–guest cyclodextrin-closo-dodecaborate dianionic complexes χCD·B12X122–(χ = α, β, γ; X = H, F–I). Here, photodechment photoelectron spectroscopy reveals the existence of two distinctly different RCBs, derived from detaching electrons from the guest dianions (RCB1) or ionizing the host neutrals (RCB2), respectively, with the latter being substantially smaller than the former. In conclusion, theoretical calculations support the duality of RCBs in these complexes and further exhibit highly anisotropic nature of the RCBs.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-76RL01830; FWP 16248
OSTI ID:
2035567
Report Number(s):
PNNL-SA-185596
Journal Information:
Journal of Physical Chemistry Letters, Vol. 14, Issue 30; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (51)

Effect of Internal Energy on the Repulsive Coulomb Barrier of Polyanions journal February 2012
Probing the Potential Barriers and Intramolecular Electrostatic Interactions in Free Doubly Charged Anions journal September 1998
Excited states of multiply-charged anions probed by photoelectron imaging: riding the repulsive Coulomb barrier journal January 2014
Photodetachment Spectroscopy of a Doubly Charged Anion: Direct Observation of the Repulsive Coulomb Barrier journal October 1998
Photodetachment of Gaseous Multiply Charged Anions, Copper Phthalocyanine Tetrasulfonate Tetraanion:  Tuning Molecular Electronic Energy Levels by Charging and Negative Electron Binding journal January 2000
Guiding Electron Emissions by Excess Negative Charges in Multiply Charged Molecular Anions journal December 2010
Electronic Structure and Stability of [B 12 X 12 ] 2– (X = F–At): A Combined Photoelectron Spectroscopic and Theoretical Study journal October 2017
Photodetachment of Hydrated Sulfate Doubly Charged Anions:  SO 4 2- (H 2 O) n ( n = 4−40) † journal August 2002
Bulk-Like Features in the Photoemission Spectra of Hydrated Doubly Charged Anion Clusters journal November 2001
Development of a low-temperature photoelectron spectroscopy instrument using an electrospray ion source and a cryogenically controlled ion trap journal July 2008
Imaging Intramolecular Coulomb Repulsions in Multiply Charged Anions journal August 2008
Introduction: Noncovalent Interactions journal May 2016
Spectroscopic and theoretical investigations of adenosine 5′-diphosphate and adenosine 5′-triphosphate dianions in the gas phase journal January 2013
Photoelectron spectroscopy and computational investigations of the electronic structures and noncovalent interactions of cyclodextrin- closo -dodecaborate anion complexes χ-CD·B 12 X 12 2− (χ = α, β, γ; X = H, F) journal January 2020
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal July 2007
Resonant tunneling through the repulsive Coulomb barrier of a quadruply charged molecular anion journal June 2012
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) journal July 2004
Molecular Anions Perspective journal May 2023
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
Gaseous cyclodextrin- closo -dodecaborate complexes χCD·B 12 X 12 2− (χ = α, β, and γ; X = F, Cl, Br, and I): electronic structures and intramolecular interactions journal January 2021
Rational design of an argon-binding superelectrophilic anion journal April 2019
Electron tunneling through the repulsive Coulomb barrier in photodetachment of multiply charged anions journal July 1999
A benchmark photoelectron spectroscopic and theoretical study of the electronic stability of [B 12 H 12 ] 2− journal April 2019
Multiwfn: A multifunctional wavefunction analyzer journal December 2011
Minimally augmented Karlsruhe basis sets journal December 2010
Gas-Phase Multiply Charged Anions journal November 1995
Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions journal July 2015
Erratum: Nature of the repulsive Coulomb barrier in multiply charged negative ions [Phys. Rev. A 63 , 012501 (2000)] journal March 2001
Small Multiply Charged Anions as Building Blocks in Chemistry journal January 1996
Repulsive Coulomb Barriers in Compact Stable and Metastable Multiply Charged Anions journal December 2000
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Highly Structured Water Networks in Microhydrated Dodecaborate Clusters journal December 2022
Probing the Electronic Stability of Multiply Charged Anions: Sulfonated Pyrene Tri- and Tetraanions journal July 2009
Kasha’s Rule and Koopmans’ Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion journal August 2022
Cooperativity in Noncovalent Interactions journal February 2016
Observation of negative electron-binding energy in a molecule journal July 1999
Photoelectron Spectroscopy and Theoretical Investigations of Gaseous Doubly Deprotonated 2′-Deoxynucleoside 5′-Monophosphate Dianions journal September 2021
Cresting the Coulomb Barrier of Polyanionic Metal Clusters journal March 2021
Direct optimization method to study constrained systems within density-functional theory journal August 2005
Site-Specific Photo-oxidation of the Isolated Adenosine-5′-triphosphate Dianion Determined by Photoelectron Imaging journal September 2020
Probing the intrinsic features and environmental stabilization of multiply charged anions journal January 2006
Unraveling hydridic-to-protonic dihydrogen bond predominance in monohydrated dodecaborate clusters journal January 2022
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr journal April 1994
Multiply Charged Anions in the Gas Phase journal January 2002
Photoexcitation of Adenosine 5′-Triphosphate Anions in Vacuo: Probing the Influence of Charge State on the UV Photophysics of Adenine journal May 2017
Influence of the repulsive Coulomb barrier on photoelectron spectra and angular distributions in a resonantly excited dianion journal August 2013
Electron emission from laser-heated fullerene dianions: Probing the repulsive Coulomb barrier journal April 2008
VMD: Visual molecular dynamics journal February 1996
Guanosine Dianions Hydrated by One to Four Water Molecules journal April 2022

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
electrical energy
electrostatic potential
polarization
potential energy