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Article Citation - WoS: 1Citation - Scopus: 1On the Smco Dimer: a Detailed Density Functional Theory Analysis(Amer Chemical Soc, 2010) Oymak, Hueseyin; Erkoc, SakirMaking use of 21 different exchange-correlation functionals, we performed density functional theory calculations, within the effective core potential level, to investigate some spectroscopic and electronic features of the SmCo dimer in its ground state. A particular emphasis was placed on the (spin) multiplicity of SmCo. Most of the functionals under discussion unanimously agreed that the multiplicity of SmCo should be 10. It was observed that the nature of interaction between Sm and Co atoms to form the SmCo dirtier can be described, to a good approximation, by a Lennard-Jones curve. For the multiplicity value 10, the binding energy D, was seen to be in the range 1.08-1.77 eV, while the equilibrium separation distance and the fundamental frequency were found to be r(e) = 2.975 +/- 0.035 angstrom and omega(e) = 120 +/- 10 cm(-1), respectively.Article Citation - WoS: 14Dissociative Adsorption of Water at (211) Stepped Metallic Surfaces by First-Principles Simulations(Amer Chemical Soc, 2017) Pekoz, Rengin; Donadio, DavideSteps at high-index metallic surfaces display higher chemical reactivity than close-packed surfaces and may give rise to selective adsorption and partial dissociation of water. Inspired by differential desorption experiments, we have studied the adsorption and dissociation of water clusters and one-dimensional wires on Pt(211) by density functional theory and molecular dynamics simulations. These calculations reveal that water at the step edges of Pt(211) adsorbs more weakly than at Pt(221), but partial dissociation of adsorbed water clusters is energetically competitive. We observe that the one-dimensional structure proposed experimentally can be realized only by partially dissociated water wires. In addition, weaker adsorption allows the formation of structures in which a number of water molecules detach from the step and form weak hydrogen bonds with the terrace. This study is further extended to the energetics of small water clusters on (211) surfaces of Ir, Rh, and Pd.Article Citation - WoS: 25Citation - Scopus: 28Semi-Ipn Chitosan/Peg Microspheres and Films for Biomedical Applications: Characterization and Sustained Release Optimization(Amer Chemical Soc, 2012) Gunbas, Ismail Dogan; Sezer, Umran Aydemir; Iz, Sultan Gulce; Gurhan, Ismet Deliloglu; Hasirci, NesrinMicro drug carriers are one of the efficient methods for local or systemic cancer treatment. In this study, the aim was to prepare a novel semi-interpenetrated (semi-IPN) micro system by using biocompatible chitosan (CH) and polyethylene glycol (PEG). Various combinations of the systems were prepared and loaded with a model chemotherapeutic drug, methotrexate (MTX), and the effects of composition on the properties and the release behavior of microspheres were examined. Also, the mechanical and thermal properties were examined on film forms of similar compositions. Increase in cross-linking caused a decrease in particle size of CH from 144 to 91 mu m, while the addition of PEG caused an increase up to 163 mu m. Elastic modulus values of the films first increased and then decreased parallel to PEG content. In vitro studies showed faster MTX release from semi-IPN CH-PEG microspheres as compared to pure CH ones. Promising results were obtained in the development of biodegradable drug vehicles.Article Citation - WoS: 1Citation - Scopus: 1Penta-Graphene/SnS2 Heterostructures with Z-Scheme Charge Transfer for Efficient Photocatalytic Water Splitting(Amer Chemical Soc, 2025) Nasoz, Duygu Lale; Surucu, Ozge; Wang, Xiaotian; Surucu, Gokhan; Sarac, Yasemin; Gencer, AysenurThe present study explores the photocatalytic potential of penta-graphene (PG) and SnS2 monolayers, along with their heterostructures (PG/SnS2), using Density Functional Theory (DFT). Structural analysis confirms that the PG/SnS2 heterostructure exhibits enhanced stability, efficient charge separation, and suitable band alignment. Optimized lattice parameters (3.66 & Aring; for PG and 3.88 & Aring; for SnS2) closely matched literature values, while ab initio molecular dynamics (AIMD) confirmed thermodynamic stability at 300 K. The heterostructure's band gap of 2.75 eV (HSE method) supports visible light absorption, and the band edge positions enable hydrogen and oxygen evolution reactions across pH 0 to 6. Optical analysis reveals significant visible-light absorption with an optical band gap of 1.43 eV. Additionally, this study identifies a Z-scheme charge transfer mechanism in the PG/SnS2 heterostructure, facilitated by an internal built-in electric field that drives directional charge migration, effectively enhancing electron-hole separation and suppressing recombination losses. This Z-scheme mechanism optimizes redox reactions, making PG/SnS2 a highly efficient photocatalyst for solar-driven hydrogen production. Furthermore, the effect of water solvent is investigated, and it reveals that this heterostructure is stable under water solvent, having suitable band edges for the photocatalytic water splitting. These findings highlight the PG/SnS2 heterostructure as a promising candidate for sustainable hydrogen generation, offering a new perspective for the design of next-generation 2D photocatalytic materials.Article Citation - WoS: 19Citation - Scopus: 18Deviations From Born-Oppenheimer Theory in Structural Chemistry: Jahn-Teller, Pseudo Jahn-Teller, and Hidden Pseudo Jahn-Teller Effects in C3h3< and C3h3<(Amer Chemical Soc, 2013) Kayi, H.; Garcia-Fernandez, P.; Bersuker, I. B.; Boggs, J. E.The electronic structure and vibronic coupling in two similar molecular systems, radical C3H3 and anion C3H3-, in ground and excited states, are investigated in detail to show how their equilibrium structures, in deviation from the Born-Oppenheimer approximation, originate from the vibronic mixing of at least two electronic states, producing the Jahn-Teller UT), pseudo JT (PJT), and hidden PJT effects. Starting with the high-symmetry geometry D3h of C3H3, we evaluated its 2-fold degenerate ground electronic state 2E" and two lowest excited states 2A,' and 2E' and found that all of them contribute to the distortion of the ground state via the JT vibronic coupling problem E" e' and two PJT problems (E" + A(1)') circle star e" and (E" + E') circle times (a2" + e"); all the three active normal modes e'(1335 e"(1030 cm(-1)), and a2"(778 cm(-1)) are imaginary, meaning that all the three vibronic couplings are sufficiently strong to cause instability, albeit in different directions. The first of them, the ground state JT effect, enhances one of the C-C bonds (toward an ethylenic form with C-2v symmetry), while the two PJT effects produce, respectively, cis (a(2)" toward C-3v symmetry) and trans (e") puckering of the hydrogen atoms. As a result, C3H3 has two coexisting equilibrium configurations with different geometry. In the C3H3- anion, the ground electronic state in DA symmetry is an orbitally nondegenerate spin triplet (3)A(2)' with a group of close in energy singlet and triplet excited states in the order of (1)A(1),', (3)A(1)', E-1", E-3", and E-1'. This shows that two PJT couplings, (3A(2)' + (3)A(1)") circle times a(2)" and (3A2' + 3E") e", may influence the geometry of the equilibrium structure in the 3A2' state. Indeed, both vibrational modes, a(2)"(1034 cm(-1)) and e"(1284 cm(-1)), are imaginary in this state. Similar to the radical case, they produce, respectively, cis (a(2)") and trans (e") puckering of the hydrogen atoms, but no e' distortion of the basic C-3 triangle; the equilibrium configuration with Cs symmetry occurs along the stronger e" distortions. Another higher-in-energy triplet-state minimum with C-2v symmetry emerges as a result of a strong JTE in the excited 3E" electronic state. In addition to these APES minima with spin-triplet electronic states, the system has a coexisting minimum with a spin-singlet electronic state, which is shown to be due to the hidden PJT effect that couples two singlet excited states. The two lowest equilibrium configurations of the C3H3- anion with different geometry and spin realize a (common to all electronic e(2) configurations) magnetic and structural bistability accompanied by a spin crossover. Some general spectroscopic consequences are also noted. As a whole, this article is intended to demonstrate the efficiency of the vibronic coupling approach in rationalizing the origin of complicated structural features of molecular systems as due to a combination of nonadiabatic JT effects.Article Citation - WoS: 24Citation - Scopus: 23Revealing the Effects of Defect States on the Nonlinear Absorption Properties of the Tlinsse and Tl2in2< Crystals in Near-Infrared Optical Limiting Applications(Amer Chemical Soc, 2024) Dogan, Anil; Karatay, Ahmet; Isik, Mehmet; Yildiz, Elif Akhuseyin; Gasanly, Nizami Mamed; Elmali, AyhanThe present study represents the effect of defect states on the nonlinear absorption and optical limiting performances of TlInSSe and Tl2In2S3Se single crystals with near-infrared excitations. The band gap energies were 2.2 and 2.22 eV, and the Urbach energies were 0.049 and 0.034 eV for TlInSSe and Tl2In2S3Se, respectively. The trapping time of localized defect states was found to be 8 ns by femtosecond transient absorption measurements. The analysis of open-aperture Z-scan data depends on two different fitting models to determine the effect of defect states on the nonlinear absorption (NA) properties of the studied crystals. Model 1 only considers two-photon absorption (TPA), while model 2 includes one-photon absorption (OPA), TPA, and free carrier absorption (FCA). The NA coefficients (ss(eff)) obtained from model 2 are higher than the values (ss) obtained from model 1 at the same intensities, revealing that defect states contribute to NA through OPA. The optical limiting properties of the TlInSSe and Tl2In2S3Se crystals were examined under 1064 nm wavelength excitation. The limiting thresholds were found to be 1.16 and 0.27 mJ/cm(2) at 29.8 GW/m(2) and 99.5 GW/m(2) input intensities, respectively. The results show that TlInSSe and Tl2In2S3Se crystals have promising potential for near-infrared optical limiting applications.Article Citation - WoS: 10Citation - Scopus: 11Capture of Carbonyl Sulfide by Organic Liquid Mixtures: a Systematic Dft Investigation(Amer Chemical Soc, 2021) Abduesslam, Mahmoud; Kayi, HakanPotential use of organic liquid mixtures consisting of amines, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), and linear alcohols (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol) in the capture of carbonyl sulfide is comprehensively and systematically investigated by density functional theory calculations at the omega B97X-D3/6-311+ +G(d,p) level of theory. In total, eighteen different systems as a combination of amines and alcohols are taken into account. A modified single-step, termolecular reaction mechanism among amine, alcohol, and carbonyl sulfide is considered. The findings from structural, thermodynamic, and kinetic analyses indicated that suggested reaction mechanisms for the eighteen different systems being studied are thermodynamically feasible, and the organic liquid mixture of BTMG with methanol yields the lowest energy barrier and the highest reaction rate constant in the capture of carbonyl sulfide.Article Citation - WoS: 7Citation - Scopus: 7Multifunctional Oxygen-Generating Nanoflowers for Enhanced Tumor Therapy(Amer Chemical Soc, 2023) Sun, Wanru; Xiao, Huifang; Zhu, Jiazhi; Hao, Zhaokun; Sun, Jian; Wang, Deqiang; Wang, RanranSonodynamic therapy (SDT) and chemotherapy have received great attention as effective methods for tumor treatment. However, the inherent hypoxia of the tumor greatly hinders its therapeutic efficacy. In this work, a tumor microenvironment-responsive biodegradable nanoplatform SiO2-MnO2-PEG-Ce6&DOX (designated as SMPC&D) is fabricated by encapsulating manganese oxide (MnO2) into silica nanoparticles and anchoring poly(ethylene glycol) (PEG) onto the surface for tumor hypoxia relief and delivery, then loaded with sonosensitizer Chlorin e6 (Ce6) and chemotherapeutic drug doxorubicin (DOX) for hypoxic tumor treatment. We evaluated the physicochemical properties of SMPC&D nanoparticles and the tumor therapeutic effects of chemotherapy and SDT under ultrasound stimulation in vitro and in vivo. After endocytosis by tumor cells, highly expressed glutathione (GSH) triggers biodegradation of the nanoplatform and MnO2 catalyzes hydrogen peroxide (H2O2) to generate oxygen (O-2), thereby alleviating tumor hypoxia. Depleting GSH and self-supplying O-2 effectively improve the SDT efficiency both in vitro and in vivo. Ultrasonic stimulation promoted the release and cellular uptake of chemotherapy drugs. In addition, the relieved hypoxia reduced the efflux of chemotherapy drugs by downregulating the expression of the P-gp protein, which jointly improved the effect of chemotherapy. This study demonstrates that the degradable SMPC&D as a therapeutic agent can achieve efficient chemotherapy and SDT synergistic therapy for hypoxic tumors.
