We present the catecholate monoanion as a new model system for the study of multidimensional tunneling. It has a symmetrical O-H double-well structure, and the H atom motion between the two wells is coupled to both low and high frequency modes with different strengths. With a view to studying mode-specific tunneling in the catecholate monoanion, we have developed a full (33) dimensional potential energy surface in transition state (TS) normal modes using a Distributed Gaussian Empirical Valence Bond (DGEVB) based approach. We have computed eigenstates in different subspaces using both unrelaxed and relaxed potentials based on the DGEVB model. With unrelaxed potentials, we present results up to 7D subspaces that include the imaginary frequency mode and six modes coupled to it. With relaxed potentials, we focus on the two most important coupling modes. The structures of the ground and vibrationally excited eigenstates are discussed for both approaches and mode-specific tunneling splitting and their trends are presented.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d1cp04590c | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Density Functional Theory-Guided Photo-Triggered Anticancer Activity of Curcumin-Based Zinc(II) Complexes.
J Phys Chem B
December 2023
Department of Chemistry, Indian Institute of Technology (BHU), Varanasi, Uttar Pradesh 221005, India (Email:
Photodynamic therapy (PDT) has evolved as a new therapeutic modality for cancer treatment with fewer side effects and drug resistance. Curcumin exhibits PDT activity, but its low bioavailability restricts its clinical application. Here, the bioavailability of curcumin was increased by its complex formation with the Zn(II) center.
View Article and Find Full Text PDFAntibacterial Photodynamic Therapy by Zn(II)-Curcumin Complex: Synthesis, Characterization, DFT Calculation, Antibacterial Activity, and Molecular Docking.
Chembiochem
January 2024
Department of Chemistry, Indian Institute of Technology (BHU), 221005, Varanasi, Uttar Pradesh, India.
The increase in antibacterial drug resistance is threatening global health conditions. Recently, antibacterial photodynamic therapy (aPDT) has emerged as an effective antibacterial treatment with high cure gain. In this work, three Zn(II) complexes viz.
View Article and Find Full Text PDFModeling Reactivity of Nitrite and Nitrous Acid at a Phenolate Bridged Dizinc(II) Site: Insights into NO Signaling at Zinc.
Chemistry
October 2023
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM), Thiruvananthapuram, 695551, India.
Although nitrite-to-NO transformation at various transition metals including Fe and Cu are relatively well explored, examples of such a reaction at the redox-inactive zinc(II) site are limited. The present report aims to gain insights into the reactivity of nitrite anions, nitrous acid (HONO), and organonitrite (RONO) at a dizinc(II) site. A phenolate-bridged dizinc(II)-aqua complex [L Zn (OH )] (ClO ) (1 -Aq, where L =tridentate N,N,O-donor monoanionic ligand) is illustrated to react with BuONO to provide a metastable arene-nitrosonium charge-transfer complex 2 .
View Article and Find Full Text PDFPolypyridyl Co -Curcumin Complexes as Photoactivated Anticancer and Antibacterial Agents.
Chembiochem
May 2023
Department of Chemistry, Indian Institute of Technology (BHU), Varanasi, Uttar Pradesh, 221005, India.
Four new Co complexes, [Co(bpy) (acac)]Cl (1), [Co(phen) (acac)]Cl (2), [Co(bpy) (cur)]Cl (3), [Co(phen) (cur)]Cl (4), where bpy=2,2'-bipyridine (1 and 3), phen=1,10-phenanthroline (2 and 4), acac=acetylacetonate (1 and 2), cur=curcumin monoanion (3 and 4) have been designed, synthesized and fully characterized. The X-ray crystal structures of 1 and 2 indicated that the CoN O core has a distorted octahedral geometry. The photoactivity of these complexes was tuned by varying the π conjugation in the ligands.
View Article and Find Full Text PDFWavepacket dynamical study of H-atom tunneling in catecholate monoanion: the role of intermode couplings and energy flow.
Phys Chem Chem Phys
January 2023
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560012, India.
We present a study of H-atom tunneling in catecholate monoanion through wavepacket dynamical simulations. In our earlier study of this symmetrical double-well system [, 2022, , 10887], a limited number of transition state modes were identified as being important for the tunneling process. These include the imaginary frequency mode , the CO scissor mode , and the OHO bending mode .
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!