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Benchmarking Quantum Chemical Methods for Optical Absorption in Boron Wheels.

ABSTRACT: We benchmark various quantum chemical methods for calculating the optical absorption in planar boron wheel clusters. The geometries of neutral planar boron wheels B7, B8, and B9 clusters are optimized at the coupled-cluster singles doubles level of theory. The optical absorption spectra of these clusters are calculated using three wave-function-based methods, namely, configuration interaction singles, random phase approximation, and equation-of-motion coupled-cluster singles doubles (EOM-CCSD) as well as using a time-dependent density-functional-theory-based method using various hybrid and long-range-corrected exchange and correlation functionals. There is an ample variation in the optical absorption spectra computed using different density functionals. When compared to the EOM-CCSD spectrum, an excellent agreement is provided by CAM-B3LYP functional, followed by ?B97xD functional. PBE0, B3LYP, and B3PW91 functionals agree among each other. However, their spectra are red-shifted with respect to the EOM-CCSD counterpart. On the basis of the natural transition orbital analysis, the nature of optical excitation is also discussed.

SUBMITTER: Shinde R

PROVIDER: S-EPMC6640779 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

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Benchmarking Quantum Chemical Methods for Optical Absorption in Boron Wheels.

Shinde Ravindra R

ACS omega 20161013 4

We benchmark various quantum chemical methods for calculating the optical absorption in planar boron wheel clusters. The geometries of neutral planar boron wheels B7, B8, and B9 clusters are optimized at the coupled-cluster singles doubles level of theory. The optical absorption spectra of these clusters are calculated using three wave-function-based methods, namely, configuration interaction singles, random phase approximation, and equation-of-motion coupled-clu ...[more]

PMID: 31457148

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Project description:Toxic metals present in drinking water pose a serious threat to the environment and human beings when present in abundance. In this work, we investigated the sensing ability of quantum dots (pristine CQDs, boron/nitrogen/sulphur (B/N/S)-doped CQDs, and BNQDs) of various sizes and morphologies (rectangular, circular, and triangular) towards toxic metals such as arsenic (As), cobalt (Co), nickel (Ni), copper (Cu), and lead (Pb) using quantum chemical density functional theory calculations in both gas and water phases. We probed the structural, electronic, and optical properties of the QDs. All the modelled QDs are energetically stable. Frontier molecular orbital analysis predicted that BNQDs are more chemically stable than all other CQDs. UV-vis absorption and Raman spectra analyses helped to understand the optical properties of all the QDs. Further, adsorption studies revealed that triangular pristine CQDs and sulphur-doped CQDs show higher adsorption affinity towards the toxic metals. The magnitude of adsorption energies follows the trend Ni > Pb > As > Cu > Co in most of the QDs. Several pristine and doped CQDs exhibited chemisorption towards the toxic metals, and hence, they can be used as adsorbents. However, a majority of BNQDs showed physisorption towards the metals, and therefore, they can be used as efficient optical sensors compared to CQDs. Further, the sensing ability of the QDs was explored through optical phenomena such as changes in UV-vis absorption spectra and fluorescence after metal adsorption. When compared to pristine CQDs and B/N/S-doped CQDs, metal complexation caused significant changes in the UV-vis absorbance peak intensities in BNQDs along with peak shifts. Moreover, metal interaction with the QDs increased their fluorescence lifetime with the highest values observed in Co-adsorbed triangular H18C46 (152.30 ns), Pb-adsorbed rectangular H15C30S (21.29 ns), and As-adsorbed circular B27N27H18 (2.99 μs) among pristine CQDs, B/N/S-doped CQDs, and BNQDs, respectively. Overall, we believe that our first-of-its-kind computational prediction of the optical sensing ability of tailor-made zero-dimensional systems such as QDs will be a great aid for experimentalists in designing novel and rapid optical probes to detect toxic metals in drinking water.

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Benchmarking Quantum Chemical Methods for Optical Absorption in Boron Wheels.

Publications

Benchmarking Quantum Chemical Methods for Optical Absorption in Boron Wheels.

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