Communication: Low-energy free-electron driven molecular engineering: <i>In situ</i> preparation of intrinsically short-lived carbon-carbon covalent dimer of CO

Davis, Daly; Sajeev, Y.

doi:10.1063/1.4976969

Cited by 10 publications

(14 citation statements)

References 26 publications

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“…83 These authors showed that a quantum charge delocalization process, similar to the one proposed in Scheme 1, can induce reactions in S−S bonded molecular chains physisorbed on a metal surface. Since then, two other theoretical papers have appeared on this subject 86,87 and reactions catalyzed by a single electron have been observed in the production of CO 2 from formic acid. 88 Finally, we note that in an aqueous solution of cisplatin-DNA complexes, hydrated electrons and hydroxyl radicals strongly react at the site of platination, 89,90 which could further increase locally the formation of single and cluster damage.…”

Section: ■ Resultsmentioning

confidence: 99%

Role of Transient Anions in Chemoradiation Therapy: Base Modifications, Cross-Links, and Cluster Damages Induced to Cisplatin-DNA Complexes by 1–20 eV Electrons

et al. 2020

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The molecular mechanism of platinum-based drugs in concomitant chemoradiation therapy relies on enhancement of DNA damage in cancer cells, particularly that of detrimental clustered lesions and cross-links induced by the abundant low-energy electrons (LEEs) generated by ionizing radiation. We provide the complete 1−20 eV electron-energy dependence of the yields of all conformational LEE-induced lesions to biological DNA, when it binds to five molecules of the chemotherapeutic drug cisplatin. Recording at 1 eV intervals clearly show that the enhancement of all lesions is particularly intense at the energies of coreexcited transient molecular anions (i.e., TMAs at 5, 6, and 10 eV). New TMAs are observed at 14 and 18 eV, only in yield functions of cisplatin-DNA complexes. Enhancements of all lesions by cisplatin are quantified over the 1−20 eV range, where maxima appear at 14 and 18 eV. The most detrimental lesions to cell survival exhibit the highest enhancements by factors of 2−3. Whereas no cluster lesions are induced by electrons of energy <5 eV in DNA, LEEs of any energy cause clustered damages in the complex. These results confirm the current notion that LEEs and TMAs play a dominant role in the molecular mechanism of platinum-drug chemoradiation therapy.

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Section: ■ Resultsmentioning

confidence: 99%

Role of Transient Anions in Chemoradiation Therapy: Base Modifications, Cross-Links, and Cluster Damages Induced to Cisplatin-DNA Complexes by 1–20 eV Electrons

et al. 2020

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“…Second, being within the same set of diagonalization of the effective Hamiltonian permits us to find all resonances lying inside the chosen energy region. These two unique features make CAP-FSCC and CIP-FSCC potentially useful for studying low-energy electron-controlled chemical reactions ,,− and for the computation of complex conical interesctions …”

Section: Perspectivesmentioning

confidence: 99%

“…The ultimate reactive species, which causes chemical reactions to eventuate, is the low-energy free electron. ,,− The negative ion resonance states formed due to the resonance capture of low-energy electrons by target molecules are reactive states, which can further undergo chemical reactions. The reactivity of molecules varies with respect to negative ion resonance states (see Figure ).…”

Section: Perspectivesmentioning

confidence: 99%

“…There has been a revival of interest in the electronic structure of negative ion resonance states in chemistry due to the recent experimental and theoretical demonstration that chemical reactions can be initiated, − controlled, − and catalyzed − through negative ion resonance states. The state-specified electron-molecule compounds for this purpose are site-specifically created on the molecular target by tuning the kinetics of low-energy free electrons. − Therefore, the computation of the kinetic energy of the free electron at which the electron-molecule compound state is formed, the lifetime of the compound state, and the electronic potential energy surfaces of the compound states become of utmost importance for the theoretical description of these free-electron induced chemical processes.…”

Section: Introductionmentioning

confidence: 99%

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Negative Ion Resonance States: The Fock-Space Coupled-Cluster Way

et al. 2020

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The negative ion resonance states, which are electronmolecule metastable compound states, play the most important role in free-electron controlled molecular reactions and low-energy free-electroninduced DNA damage. Their electronic structure is often only poorly described but crucial to an understanding of their reaction dynamics. One of the most important challenges to current electronic structure theory is the computation of negative ion resonance states. As a major step forward, coupled-cluster theories, which are well-known for their ability to produce the best approximate bound state electronic eigen solutions, are upgraded to offer the most accurate and effective approximations for negative ion resonance states. The existing Fock-space coupled-cluster (FSCC) and the equation-ofmotion coupled-cluster (EOM-CC) approaches that compute bound states are redesigned for the direct and simultaneous determination of both the kinetic energy of the free electron at which the electron-molecule compound states are resonantly formed and the corresponding autodetachment decay rate of the electron from the metastable compound state. This Feature Article reviews the computation of negative ion resonances using the FSCC approach and, in passing, provides the highlights of the equivalent EOM-CC approach.

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“…Carbon (C) and oxygen (O) are key elements on earth and in space. Clusters constituted simply by them form a special class of oxides of carbon, namely oxocarbons(Rubin and Gleiter, 2000; Horiuchi et al, 2010; Kikuchi et al, 2014; Davis and Sajeev, 2017; Wang et al, 2018a). The huge energy release from C n O n to nCO provides great promise that a kinetically stabilized C n O n might find applications in the so-called high-energy density materials (HEDMs) (Schmidt et al, 2000; Gambi et al, 2001; Corkran and Ball, 2004; Xia et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

Xin

Han

et al. 2019

Front. Chem.

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Despite the great interest in energy storage application, stable neutral C n O n ( n > 1) structures either in thermodynamics or kinetics have yet been largely limited due to the rather high tendency to release the very stable CO molecule. The neutral cyclopropanetrione (C 3 O 3 ) cluster has long remained elusive since no isomer with sufficient kinetic stability has been found either experimentally or theoretically. In this work, we constructed the first global potential energy surface of singlet C 3 O 3 at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level, from which the kinetic stability of a wide range of C 3 O 3 isomers can be determined by investigating their isomerization and fragmentation pathways. Amongst, a three-membered ring structure 01 is the global C 3 O 3 isomer with a barrier of 10.6 kcal/mol at the sophisticated W1BD level. In particular, two carbene-type isomers 02 and 04 possess appreciable destruction barriers of 20.3 and 24.7 kcal/mol at W1BD, respectively. Thus, 02 and 04 can be useful building blocks for constructing larger high-energy density carbon-oxygen clusters. Moreover, with the carbene center, both might effectively functionalize various nano-materials while retaining the electrochemical active carbonyl and epoxyl moieties that are very desirable in alkali metal-ion batteries.

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Communication: Low-energy free-electron driven molecular engineering: In situ preparation of intrinsically short-lived carbon-carbon covalent dimer of CO

Cited by 10 publications

References 26 publications

Role of Transient Anions in Chemoradiation Therapy: Base Modifications, Cross-Links, and Cluster Damages Induced to Cisplatin-DNA Complexes by 1–20 eV Electrons

Role of Transient Anions in Chemoradiation Therapy: Base Modifications, Cross-Links, and Cluster Damages Induced to Cisplatin-DNA Complexes by 1–20 eV Electrons

Negative Ion Resonance States: The Fock-Space Coupled-Cluster Way

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers

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