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Prediction of tetraoxygen reaction mechanism with sulfur atom on the singlet potential energy surface.

ABSTRACT: The mechanism of S+O? (D(?h)) reaction has been investigated at the B3LYP/6-311+G(3df) and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O? (D(?h)) reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with -188.042 and -179.147?kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the ¹S+¹O? (D(?h)) atmospheric reactions.

SUBMITTER: Khademzadeh A

PROVIDER: S-EPMC3920618 | biostudies-literature | 2014

REPOSITORIES: biostudies-literature

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Prediction of tetraoxygen reaction mechanism with sulfur atom on the singlet potential energy surface.

Khademzadeh Ashraf A Vahedpour Morteza M Karami Fereshte F

TheScientificWorldJournal 20140123

The mechanism of S+O₄ (D(₂h)) reaction has been investigated at the B3LYP/6-311+G(3df) and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O₄ (D(₂h)) reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with -188.042 and -179.147 kcal/mol in Gibbs free ener ...[more]

PMID: 24587763

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Project description:Heavy-atom-free sensitizers forming long-living triplet excited states via the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process have recently attracted attention due to their potential to replace costly transition metal complexes in photonic applications. The efficiency of SOCT-ISC in BODIPY donor-acceptor dyads, so far the most thoroughly investigated class of such sensitizers, can be finely tuned by structural modification. However, predicting the triplet state yields and reactive oxygen species (ROS) generation quantum yields for such compounds in a particular solvent is still very challenging due to a lack of established quantitative structure-property relationship (QSPR) models. In this work, the available data on singlet oxygen generation quantum yields (ΦΔ ) for a dataset containing >70 heavy-atom-free BODIPY in three different solvents (toluene, acetonitrile, and tetrahydrofuran) were analyzed. In order to build reliable QSPR model, a series of new BODIPYs were synthesized that bear different electron donating aryl groups in the meso position, their optical and structural properties were studied along with the solvent dependence of singlet oxygen generation, which confirmed the formation of triplet states via the SOCT-ISC mechanism. For the combined dataset of BODIPY structures, a total of more than 5000 quantum-chemical descriptors was calculated including quantum-chemical descriptors using density functional theory (DFT), namely M06-2X functional. QSPR models predicting ΦΔ values were developed using multiple linear regression (MLR), which perform significantly better than other machine learning methods and show sufficient statistical parameters (R=0.88-0.91 and q2 =0.62-0.69) for all three solvents. A small root mean squared error of 8.2 % was obtained for ΦΔ values predicted using MLR model in toluene. As a result, we proved that QSPR and machine learning techniques can be useful for predicting ΦΔ values in different media and virtual screening of new heavy-atom-free BODIPYs with improved photosensitizing ability.

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Prediction of tetraoxygen reaction mechanism with sulfur atom on the singlet potential energy surface.

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Prediction of tetraoxygen reaction mechanism with sulfur atom on the singlet potential energy surface.

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