Cl2 Molecules Research Articles

Exploring penta-ZnS2 monolayer as potential gas sensor for toxic gases based on first principles

To gain a deeper understanding of the application of ZnS2 monolayer in gas sensors, this paper predicts the electronic properties and gas sensing performance of CO, CH4, Cl2, H2S, NO and NH3 gas molecules adsorbed on ZnS2 monolayer based on first principles research. The results show that ZnS2 is sensitive to CO, Cl2, H2S, NO and NH3 by chemisorption and to CH4 by strong physisorption. The adsorption of gases effectively changes the electronic properties and gas sensing properties on ZnS2, and the bandgap of the adsorbed system changes significantly compared with the intrinsic ZnS2, and the characteristics of the work function can effectively distinguish various gases. Our calculations are of great significance for exploring the sensing applications of ZnS2 monolayer as a new member of the gas sensor family, and we expect that this work will provide new perspectives and theoretical foundations for the possible applications of ZnS2 monolayer in the sensing and processing of CO, CH4, Cl2, H2S, NO and NH3 gases.

Facile heterolytic bond splitting of molecular chlorine upon reactions with Lewis bases: Comparison with ICl and I2.

Formation of molecular complexes and subsequent heterolytic halogen-halogen bond splitting upon reactions of molecular Cl2 with nitrogen-containing Lewis bases (LB) are computationally studied at M06-2X/def2-TZVPD and for selected compounds at CCSD(T)/aug-cc-pvtz//CCSD/aug-cc-pvtz levels of theory. Obtained results are compared with data for ICl and I2 molecules. Reaction pathways indicate, that in case of Cl2∙LB complexes the activation energies for the heterolytic Cl-Cl bond splitting are lower than the activation energies of the homolytic splitting of Cl2 molecule into chlorine radicals. The heterolytic halogen splitting of molecular complexes of X2∙Py with formation of [XPy2]+… contact ion pairs in the gas phase is slightly endothermic in case of Cl2 and I2, but slightly exothermic in the case of ICl. Formation of {[ClPy2]+… }2 dimers makes the overall process exothermic. Taking into account that polar solvents favor ionic species, generation of donor-stabilized Cl+ in the presence of the Lewis bases is expected to be favorable. Thus, in polar solvents the oxidation pathway via donor-stabilized Cl+ species is viable alternative to the homolytic Cl-Cl bond breaking.

Development of a ReaxFF Reactive Force Field for Pt/Cl Systems with Application to Platinum Metal Etching with Chlorine and Hydrogen Chloride Gases.

In this study, we present the development of a ReaxFF Pt/Cl/H reactive force field designed to elucidate the etching process by Cl for Pt surfaces. The ReaxFF force field parameters were optimized based on a quantum mechanical training set, which included adsorption energies of Cl and dissociation of HCl on Pt(100) and Pt(111) surfaces, energy/volume relations of PtCl2 crystals, and Cl diffusion on Pt(100) and Pt(111) surfaces. The predictive capability of the force field was further established through molecular dynamics simulations, which investigated the interactions of Cl2 and HCl molecules with the (100) and (111) surfaces of c-Pt crystalline solid slabs. A comparative analysis revealed that the Pt (100) surface exhibited higher susceptibility to chlorination and etching, leading to a more dominant removal of surface Pt atoms, whereas the Pt (111) surface showed greater resistance to these processes. This resistance impeded the access of Cl atoms to the Pt surface, resulting in a slower formation of PtxCly molecules. The etching ratios between HCl and Cl2 were compared with experimental results, yielding satisfactory agreement. This indicates that the developed ReaxFF protocol serves as a valuable tool for studying atomistic-scale details of the etching process in platinum metal systems.

First-Principles Study on Bi2Te2S Monolayer for Adsorption Performance and Sensing Capability.

In this study, a comprehensive investigation into the gas sensing capabilities of the two-dimensional (2D) Bi2Te2S was conducted using first-principles calculations based on density functional theory. A wide array of gas molecules, including CH4, Cl2, CO, CO2, H2, H2O, H2S, N2, NH3, NO, NO2, O2, and SO2, was encompassed in this work. Through the strategic placement of these gas molecules at different locations on the Bi2Te2S monolayer and taking into account a range of configurations, the adsorption process was thoroughly investigated, with a particular emphasis on the structures that are most thermodynamically stable. It was revealed that Cl2, O2, NO, and NO2 molecules exhibit a pronounced affinity for the Bi2Te2S monolayer. Notably, it was found that the Cl2@Bi2Te2S, O2@Bi2Te2S, and NO2@Bi2Te2S systems' gas adsorption capabilities are greatly enhanced by the introduction of an external electric field. Moreover, the addition of horizontal biaxial strain significantly impacts the gas adsorption properties of the O2@Bi2Te2S system, underscoring the tunability of the Bi2Te2S monolayer's sensing capabilities. In light of these theoretical results, the Bi2Te2S monolayer is proposed to have great potential as an extremely sensitive and selective gas sensing material, especially for identifying Cl2, O2, NO, and NO2. This study clarifies the intrinsic gas sensing capabilities of the Bi2Te2S monolayer, while highlighting how its performance can be tailored in response to external stimuli, setting the stage for the advancement of more sophisticated gas sensing devices.

Adsorption behavior of Cl2 on TiC0.89O0.11(001) surface based on the first principle calculation

Based on the first-principles ab initio calculation method of density functional theory (DFT), the adsorption models of Cl2 molecules on both the TiC0.89O0.11(001) intact surface and the carbon vacancy surface were established, followed by calculations and analysis of the adsorption structures, adsorption energy, differential charge density, and density of states (DOS). The results demonstrate that the adsorption process of Cl2 molecules on the TiC0.89O0.11(001) surface involves chemical adsorption, with a higher likelihood of dissociation into Cl atoms during adsorption. These dissociated Cl atoms can potentially interact with surface Ti and/or C atoms to form Ti-Cl bonds, C-Cl bonds, Ti-Cl-C bonds, and Ti-Cl-Ti bonds. Simultaneously, the stability of the adsorbed structure is influenced by both the bonding conditions between Cl atoms and surface atoms and the position of Cl atom adsorption (e.g., whether it is located above the vacancy C). Following adsorption, there is a weakening in the bonding strength of Ti-C or Ti-O bonds on the TiC0.89O0.11(001) surface. During the adsorption process, Cl atoms can either act as electron donors or acceptors. When the Ti-Cl bond structure is formed, Cl atoms function as electron acceptors; however, when the C-Cl bond structure is established, Cl atoms predominantly act as electron donors. Surface Ti atoms act as electron donors while surface C and O atoms function as electron acceptors. Additionally, the presence of surface carbon vacancy enhances the interaction between Cl and Ti atoms, weakens the interaction between Cl and C atoms, and attenuates the interaction between C, O, and Ti atoms in the structure. And it can augment the electron acquisition by Cl2 molecules upon adsorption, reduce the adsorption energy, and promote greater stability in the adsorption structure. All the effects contribute to facilitating TiCl4 formation.

Li-decorated B12C6N6 hybrid nanocage for sensing Cl2, COCl2, H2S and NH3 gas molecules

We examined the gas sensing abilities of Li-decorated B12C6N6 (B12C6N6Li) hybrid nanocage, introducing B12C6N6 for the first time in sensing applications. The toxic gas molecules like Cl2, COCl2, H2S, and NH3 were considered. The B12C6N6 nanocage with C2V symmetry displayed the lowest energy among its isomers. Li exhibited stronger anchoring above B3C2N ring compared to B2C2, B2N2, and B3CN2 rings of B12C6N6 nanocage, displaying a binding energy of −3.30 eV. Li decoration resulted in asymmetric spin-up and spin-down states near Fermi level, indicating magnetic nature of complexes. B12C6N6, an electron-deficient nanocage, displayed charge transfer from Li atom to the nanocage. Substantial changes in electronic states occurred following the adsorption of Cl2 and COCl2 molecules. COCl2, H2S, and NH3 adsorption is thermodynamically favourable over a wide temperature and pressure range, while Cl2 adsorption is favourable only within a confined range. Earlier findings indicate dissociative adsorption of Cl2 on nanocages rendering the substrate to be non-reusable. B12C6N6Li considered here is superior over other nanocages as Cl2 adsorbs in molecular form while B12C6N6Li also demonstrates significant sensitivity. B12C6N6Li nanocage is unsuitable for sensing H2S and NH3 gas molecules but holds promise as a potential candidate for sensing Cl2 and COCl2 gas molecules.

Surface-Grafted Single-Atomic Pt-Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor-Inducing Interfacial Electron Transfer.

Based on the electron-withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post-modification amide reaction was firstly used to graft it onto the surface of NH2-MIL-125, which performed as a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precisely regulating over the first coordination sphere of Pt single atoms was achieved using further post-modification with additional bipyridine to investigate the effect of Pt-Nx coordination numbers on reaction activity. The as-synthesized NML-PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g-1 h-1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2-MIL-125 and NML-PtN4, respectively. In addition, the superior apparent quantum yield of 4.01 % (390 nm) and turnover frequency of 190.3 h-1 (0.78 wt % Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF-Molecule catalysts with efficient charge carrier separation and precise regulation of single-atom coordination sphere.

Surface‐Grafted Single‐Atomic Pt−Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor‐Inducing Interfacial Electron Transfer

AbstractBased on the electron‐withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post‐modification amide reaction was firstly used to graft it onto the surface of NH2‐MIL‐125, which performed as a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precisely regulating over the first coordination sphere of Pt single atoms was achieved using further post‐modification with additional bipyridine to investigate the effect of Pt−Nx coordination numbers on reaction activity. The as‐synthesized NML‐PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g−1 h−1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2‐MIL‐125 and NML‐PtN4, respectively. In addition, the superior apparent quantum yield of 4.01 % (390 nm) and turnover frequency of 190.3 h−1 (0.78 wt % Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF‐Molecule catalysts with efficient charge carrier separation and precise regulation of single‐atom coordination sphere.

Efficient calculation of unbiased atomic forces in ab initio variational Monte Carlo

quantum Monte Carlo (QMC) is a state-of-the-art numerical approach for evaluating accurate expectation values of many-body wave functions. However, one of the major drawbacks that still hinders widespread QMC applications is the lack of an affordable scheme to compute unbiased atomic forces. In this study, we propose an efficient method to obtain unbiased atomic forces and pressures in the variational Monte Carlo (VMC) framework with the Jastrow-correlated Slater determinant ansatz or the Jastrow antisymmetrized geminal power ansatz, exploiting the gauge-invariant and locality properties of their geminal representation. We demonstrate the effectiveness of our method for H2 and Cl2 molecules and for the cubic boron nitride crystal. Our framework has a better algorithmic scaling with the system size than the traditional finite-difference method and, in practical applications, is as efficient as single-point VMC calculations. Thus, it paves the way to study dynamical properties of materials, such as phonons, and is beneficial for pursuing more reliable machine-learning interatomic potentials based on unbiased VMC forces. Published by the American Physical Society 2024

First Principles Investigation of C, Cl2 and CO Co-Adsorption on ZrSiO4 Surfaces for Carbochlorination Reaction.

The study of the adsorption behavior of C, CO and Cl2 on the surface of ZrSiO4 is of great significance for the formulation of the technological parameters in the carbochlorination reaction process. Based on first principles, the adsorption structure, adsorption energy, Barder charge, differential charge density, partial density of states and energy barrier were calculated to research the adsorption and reaction mechanism of C and Cl2 on ZrSiO4 surfaces. The results indicated that when C, CO and Cl2 co-adsorbed on the surface of ZrSiO4, they interacted with surface atoms and the charge transfer occurred. The Cl2 molecules dissociated and formed Zr-Cl bonds, while C atoms formed C1=O1 bonds with O atoms. Compared with CO, the co-adsorption energy and reaction energy barrier of C and Cl2 are lower, and the higher the C content, the lower the adsorption energy and energy barrier, which is beneficial for promoting charge transfer and the dissociation of Cl2. The 110-2C-2Cl2 has the lowest adsorption energy and the highest reaction activity, with adsorption energy and energy barriers of -13.45 eV and 0.02 eV. The electrons released by C are 2.30 e, while the electrons accepted by Cl2 are 2.37 e.

Ultra-thin CdTe film properties enhancement via eco-friendly MgCl2-assisted thermal treatment

AbstractThe thermal treatment of the CdTe thin film in the presence of CdCl2 is a crucial step in the creation of high-efficiency CdTe-based solar cells. The process influences the grain growth, grain boundary passivation, and doping, including CdTe recrystallization, and promotes to building of the photovoltaic junction. However, toxic Cd2+ ions released by the CdCl2, which is highly soluble in water is a major environmental concern of this process. Also, the price of CdCl2 (about 30 cents/gram) that drives up manufacturing costs is another limitation of the current processs. Finding a non-toxic Cl molecule is therefore currently in high demand and key factor for the thermal treatment of CdTe. In this study, MgCl2 was thoroughly explored as an alternative, non-toxic, and somewhat less expensive chlorine-containing chemical for CdTe thermal treatment. CdTe thin films, approximately 1.0 µm thick, were deposited on a glass substrate at 350 ºC using RF magnetron sputtering, and after deposition, different concentrations of MgCl2 (0.2 M, 0.3 M, 0.4 M, and 0.5 M) mixed with 10% methanol were applied to the films for around 10 s, forming a thin MgCl2 coating, followed by the optimized heat treatment at 400 ºC in a nitrogen–oxygen environment. We found that the thermal treatment of CdTe films using MgCl2 showed improved crystallinity, surface morphology, impurity profiles, and carrier density similar to the conventional CdCl2 process. The sample treated with 0.4 M MgCl2 exhibited the best output as obtained the band gap of nearly 1.46 eV, a refractive index of 2.84, a carrier concentration of 9.81E+15 cm−3, and mobility 35.08 cm2/V-S with a moderate resistivity. Our findings show that MgCl2 could be utilized instead of traditional CdCl2 in the current fabrication procedure, which substantially lowers the environmental hazard with a cost-effective production process of CdTe-assembled solar cells.

Enrichment of Chlorine in Porous Organic Nanocages for High-Performance Rechargeable Lithium-Chlorine Batteries.

Rechargeable Li-Cl2 batteries are recognized as promising candidates for energy storage due to their ultrahigh energy densities and superior safety features. However, Li-Cl2 batteries suffer from a short cycle life and low Coulombic efficiency (CE) at a high specific cycling capacity due to a sluggish and insufficient Cl2 supply during the redox reaction. To achieve Li-Cl2 batteries with high discharge capacity and CE, herein, we propose and design an imine-functionalized porous organic nanocage (POC) to enrich Cl2 molecules. Based on density functional theory (DFT) calculations, the imine group sites in host cages strongly interact with Cl2 molecules, facilitating the rapid capture of Cl2. As a result, the output capacity of the Li-Cl2 battery using POC (Li-Cl2@POC) is significantly boosted, achieving an ultrahigh discharge capacity of 4000 mAh/g at ∼100% CE. Benefiting from the designed POC, the highest utilization ratio of deposited LiCl at the first cycle in the Li-Cl2@POC battery reaches as high as 85%, superior to all reported values. The Li-Cl2@POC battery exhibits excellent electrochemical performance even at low temperatures, delivering stable cycling over 200 cycles under a capacity of 2000 mAh/g at -20 °C with a voltage plateau of 3.5 V and an average CE of 99.7%. We also demonstrate that the Li-Cl2@POC cells can be assembled and well-operated in a dry room, showing advantages for mass production. Our designed POC promotes the practical deployment of rechargeable Li-Cl2 batteries.

The Equilibrium Molecular Structure of Cyclic (Alkyl)(Amino) Carbene Copper(I) Chloride via Gas-Phase Electron Diffraction and Quantum Chemical Calculations.

Copper-centered carbene-metal-halides (CMHs) with cyclic (alkyl)(amino) carbenes (CAACs) are bright phosphorescent emitters and key precursors in the synthesis of the highly promising class of the materials carbene-metal-amides (CMAs) operating via thermally activated delayed fluorescence (TADF). Aiming to reveal the molecular geometry for CMH phosphors in the absence of the intermolecular contacts, we report here the equilibrium molecular structure of the (CAAC)Cu(I)Cl (1) molecule in the gas-phase. We demonstrate that linear geometry around a copper atom shows no distortions in the ground state. The structure of complex 1 has been determined using the electron diffraction method, supported by quantum chemical calculations with RI-MP2/def2-QZVPP level of theory and compared with the crystal structure determined by X-ray diffraction analysis. Mean vibrational amplitudes, uij,h1, and anharmonic vibrational corrections (rij,e • rij,a) were calculated for experimental temperature T = 20 °C, using quadratic and cubic force constants, respectively. The quantum theory of atoms in molecules (QTAIM) and natural bond order (NBO) analysis of wave function at MN15/def2TZVP level of theory revealed two Cu…H, three H…H, and one three-center H…H…H bond paths with bond critical points. NBO analysis also revealed three-center, four-electron hyperbonds, (3c4e), [π(N-C) nπ(Cu) ↔ nπ(N) π(N-Cu)], or [N-C: Cu ↔ N: C-Cu] and nπ(Cu) → π(C-N)* hyperconjugation, that is the delocalization of the lone electron pair of Cu atom into the antibonding orbital of C-N bond.

The adsorption behaviors of Cl2 on TiC (100) surface: A density functional theory study

It is important to study the adsorption behavior of Cl2 molecules on the TiC surface and the formation and transfer of reaction products to understand and to regulate the low-temperature chlorination reaction process of carbonized titanium-bearing slag. Based on the first-principles ab initio calculation method of density functional theory (DFT), the adsorption models of Cl2 molecules on the TiC (100) intact surface and the surface with carbon vacancy are established, and the adsorption structures, electronic properties, differential charge density and partial density of states (PDOS) are calculated and analyzed. The formation process and the optimal formation path of the adsorption reaction product are explored. The investigated results indicate that the Cl atoms in the system bonded to the surface Ti atoms are more stable than the structure formed by bonding to the surface C atoms. The electron flow direction is Ti → C and Ti → Cl. In the reaction of TiC with Cl2 molecules, the TiCl3 intermediate is easier to form than the TiCl2 intermediate. The energy barrier to be overcome to form the TiCl3 intermediate is lower and the energy to be supplied is easily met by external conditions. TiCl3 is then further chlorinated to form TiCl4.

Study on the sensing characteristics of two‐dimensional material WTe2 to toxic gases HF and Cl2

AbstractThe adsorption characteristics of gas molecules HF and Cl2 on monolayer WTe2 surface are studied by first‐principles calculation method. The results show that monolayer WTe2 is more sensitive to gas molecule Cl2. The adsorption performance of monolayer WTe2 to gas molecule HF cannot be improved by doping atoms. When the upward vertical electric field is applied, the sensitivity of monolayer WTe2 to gas molecule Cl2 is improved, and when the downward vertical electric field is applied, the monolayer WTe2 shows an obvious desorption trend to gas molecule Cl2. The vertical electric field cannot significantly enhance the interaction between gas molecule HF and Ag‐doped monolayer WTe2. Our research confirms that monolayer WTe2 is more sensitive to gas molecule Cl2 and can be improved or desorbed by the vertical electric field, while that of monolayer WTe2 for gas molecule HF cannot significantly change. Furthermore, the electrical transport characteristics of monolayer WTe2 and Cl2‐WTe2 system are studied to better explain the reason for the higher sensitivity to gas molecule Cl2. The research results of this paper provide theoretical guidance for the experimental preparation of high sensitivity gas sensor based on two‐dimensional transition metal dichalcogenide WTe2.

Theoretical study of 2D PbSe/Bi2Se3 heterojunctions as gas sensors for the detection of SO2 and Cl2

In this paper, we construct a two-dimensional PbSe/Bi2Se3 van der Waals heterojunction to study the adsorption of Cl2 and SO2 by this heterojunction. Based on the help of Bader charge, charge density difference diagram, and electron localization function, we find the following conclusions. Among the six configurations, three meet the requirements for semiconductor gas sensor detection materials, namely α-PbSe-Bi2Se3, β-PbSe-Bi2Se3, and Bi2Se3-γ-PbSe. The Bi surface of the configuration α-PbSe-Bi2Se3 does not break the Cl-Cl bond in the Cl2 molecule after the adsorption of Cl2, and the band gap of the adsorbed material is reduced by 73.1%. The band gap of the Pb surface of the α-PbSe-Bi2Se3, β-PbSe-Bi2Se3 and Bi2Se3-γ-PbSe configurations change significantly after the adsorption of SO2, directly changing from a narrow band gap to a metallic material with a low adsorption energy and easy desorption of SO2 from the adsorbed material. Therefore, the two-dimensional PbSe/Bi2Se3 van der Waals heterojunction has the potential to become a core detection material for Cl2 and SO2 gas sensors.

Generation of the isolated highly elliptically polarized attosecond pulse using the polarization gating technique: TDDFT approach.

This paper theoretically investigates the generation of isolated elliptically polarized attosecond pulses with a tunable ellipticity from the interaction of Cl2 molecule and a polarization-gating laser pulse. A three-dimensional calculation based on the time-dependent density functional theory is done. Two different methods are proposed for generating elliptically polarized single attosecond pulses. The first method is based on applying a single-color polarization gating laser and controlling the orientation angle of the Cl2 molecule with respect to the polarization direction of the laser at the gate window. An attosecond pulse with an ellipticity of 0.66 and a pulse duration of 275 as is achieved by tuning the molecule orientation angle to 40° in this method and superposing harmonics around the harmonic cutoff. The second method is based on irradiating an aligned Cl2 molecule with a two-color polarization gating laser. The ellipticity of the attosecond pulses obtained by this method can be controlled by adjusting the intensity ratio of the two colors. Employing an optimized intensity ratio and superposing harmonics around the harmonic cutoff would lead to the generation of an isolated, highly elliptically polarized attosecond pulse with an ellipticity of 0.92 and a pulse duration of 648 as.

Direct Chlorination of Ethene on ZnO (0001̅) by Hot Chlorine Atoms

The interaction between ethene and Cl2 on ZnO(0001̅) has been investigated using X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. At 110 K, the Cl2 molecule is perpendicularly adsorbed on ZnO(0001̅). Upon heating, Cl2 is dissociated on the surface in the temperature range of 200–230 K. When the surface coadsorbed with Cl2 and ethene is heated, the desorption of 1,2-dichloroethane is observed at ∼230 K. The desorption temperature is comparable to the dissociation temperature of Cl2 on ZnO(0001̅). Ethene does not react with Cl atoms chemisorbed on ZnO(0001̅). We propose that “hot” Cl atoms, which are produced during thermal dissociation of Cl2, promote the direct chlorination of C2H4. The energy of the hot Cl atoms is calculated to be maximum 27.5 kcal/mole higher than the energy of the chemisorbed Cl atoms.

Combining machine learning algorithm to improve prediction performance of ab initio method for vibrational energy spectra of HF/HBr/H<sup>35</sup>Cl/Na<sup>35</sup>Cl

Halides play an important role in atmospheric chemistry, corrosion of steel, and also in controlling the abundance of O<sub>3</sub>. Moreover high-precision vibrational energy spectra contain a large amount of quantum information of molecular system and are basic data for people to understand and manipulate molecules. At present, ab-initio methods have achieved many calculation results of the potential energy surfaces and corresponding vibrational energy of molecules, but they still face challenges in terms of accuracy and computational cost. Recently, data-driven machine learning methods have demonstrated very strong capability of extracting high-dimensional functional relationships from massive data and have been widely used in spectrum studies. ​Therefore, a theoretical approach to combining ab-initio method and machine learning algorithm is presented here to predict the vibrational energy of diatomic systems, which improves the accuracy and simultaneously reduces the computational cost. Firstly, the vibrational energy levels of 42 diatomic molecules are obtained by using different CCSD(T) methods to calculate the configurations from simple to complex and the corresponding experimental results are also collected. ​A machine learning algorithm is then used to learn the difference between the CCSD(T) method calculated vibrational results and the experimental vibrational results, and a high-dimensional error function is finally constructed to improve the original CCSD(T) computational accuracy. The results for HF, HBr, H<sup>35</sup>Cl and Na<sup>35</sup>Cl (they did not appear in the training set) and other halogen molecules show that compared with the CCSD(T)/cc-pV5Z calculation method alone, the present method reduces the prediction error by more than 50% and the computational cost by nearly one order of magnitude. It is worth noting that the method proposed in this paper is not only limited to the energy level prediction of diatomic systems, but also applicable in other fields where data can be obtained by ab initio methods and experimental methods simultaneously, such as the energy spectrum properties of macromolecular systems.

Isobaric molar heat capacity model for the improved Tietz potential

AbstractIn this study, the improved Tietz potential was used to describe the internal vibration of diatomic molecules. By employing the expression for upper bound vibrational quantum number and canonical partition function of the system, equation for the prediction of constant pressure (isobaric) molar heat capacity of diatomic molecules was derived. The analytical model was used to predict the isobaric molar heat capacity of the ground state CO, BBr, HBr, HI, P2, KBr, Br2, PBr, SiO, and Cl2 molecules. The upper bound vibrational quantum number obtained for the molecules are 85, 100, 21, 21, 115, 301, 89, 157, 110, and 67. The calculated average absolute deviations are 2.3462%, 1.1342%, 2.3350%, 1.9078%, 0.7268%, 2.4041%, 1.7849%, 1.8989%, 2.5209%, and 2.1523% from experimental data. The results obtained are in good agreement with available literature data on gaseous molecules.