Tian Lu

Tian Lu
Beijing Kein Research Center for Natural Sciences

PhD

About

108
Publications
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Introduction

Publications

Publications (108)
Article
Full-text available
Novel nanowire technologies encompass the use of metals and crystals with a high electric transport potential and superior charge-collection properties. However, nanowires built on metals such as cadmium, gallium-arsenide and similar alloys present serious environmental and health risks. The use of carbon is a far more environmentally friendly solu...
Article
Understanding the nature of noncovalent interactions between nonpolar small molecules is not only theoretically interesting but also important for practical purposes. The interaction mechanism of three prototype dimers (H2)2, (N2)2, and (H2)(N2) are investigated by state-of-the-art quantum chemistry calculations and energy decomposition analysis. I...
Article
Bond order is an important concept for understanding the nature of chemical bond. In this work, we propose a novel definition of bond order, called Laplacian bond order (LBO), which is defined as a scaled integral of negative parts of Laplacian of electron density in fuzzy overlap space. Many remarkable features of LBO are exemplified by numerous s...
Article
Full-text available
Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5...
Article
Escherichia coli tyrosine kinase (Etk) regulates the export of pathogenic capsular polysaccharide (CPS) by intermolecularly autophosphorylating its C-terminal tyrosine cluster. The kinase Etk, however, needs to be first activated by the intramolecular phosphorylation of a tyrosine residue, Y574, next to the active site. The recently determined stru...
Preprint
Cyclocarbon fully consists of sp-hybridized carbon atoms, which shows quite unusual electronic and geometric structures compared to common molecules. In this work, we systematically studied strain energy (SE) of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)...
Chapter
Multiwfn is an open‐source, freely available post‐processing software aiming for analyzing the electronic structure of molecular systems. Electronic wave function produced by most mainstream quantum chemistry programs can be processed. Performing analysis of conceptual density functional theory (CDFT) is one of the important applications of Multiwf...
Article
The electronic spectra and (hyper)polarizability of C18-(CO)n (n = 2, 4, and 6) are studied using theoretical calculations to reveal the effect of introducing carbonyl (-CO) groups on the molecular optical properties. Successive introduction of -CO groups is observed to cause a red-shift in the absorption spectrum, but maximum absorption of all mol...
Article
The powerful independent gradient model (IGM) method has been increasingly popular in visual analysis of intramolecular and intermolecular interactions in recent years. However, we frequently observed that there is an evident shortcoming of IGM map in graphically studying weak interactions, that is its isosurfaces are usually too bulgy; in these ca...
Preprint
Concentration variation of chemical substances in complex reactions is of great chemical interest, because many valuable information about reaction, such as half-life time, dependency of reaction rate on barriers, main product of competitive reactions, the order of appearance of various substances, can be directly studied by examining time-dependen...
Preprint
The photophysical property and optical nonlinearity of an electronic push-pull mesoionic compond, 2-(4-trifluoromethophenyl)-3-methyl-4-(4-methoxyphenyl)-1,3-thiazole-5-thiolate, were theoretically investigated with a reliable computing strategy. The essence of the optical properties were then explored through a variety of wavefunction analysis met...
Preprint
Full-text available
Analysis of electronic wavefunction generated by quantum chemistry codes has crucial role in exploring nature of electronic structure and providing valuable information of chemical interest. A file containing wavefunction information is inevitably needed as a communicator between wavefunction analysis codes and quantum chemistry programs. There hav...
Article
The bonding character, electron delocalization, and aromaticity of the cyclo[18]carbon (C 18 ) precursors, C 18 -(CO) n ( n = 6, 4, and 2), are studied by combining quantum chemical calculations and various electronic wavefunction analyses with different physical bases. It is found that C 18 -(CO) n ( n = 6, 4, and 2) molecules exhibit alternating...
Preprint
Full-text available
The independent gradient model (IGM) originally proposed in Phys. Chem. Chem. Phys., 19, 17928 (2017) has been increasingly popular in visual analysis of intramolecular and intermolecular interactions in recent years, and it has many clear advantages over the widely employed noncovalent interaction (NCI) method, such as intrafragment and interfragm...
Preprint
Full-text available
The independent gradient model (IGM) originally proposed in Phys. Chem. Chem. Phys., 19, 17928 (2017) has been increasingly popular in visual analysis of intramolecular and intermolecular interactions in recent years, and it has many clear advantages over the widely employed noncovalent interaction (NCI) method, such as intrafragment and interfragm...
Article
Recently, Iyakutti and coworkers published an interesting paper studying characteristics of cyclo[12]carbon and cyclo[18]carbon as well as their interactions with graphene (Mater. Sci. and Eng. B 263 (2021) 114895). However, we found some of their calculations are obviously unreasonable and a few conclusions are misleading. Here, we make some remar...
Article
Doping alkali metal atoms, especially lithium (Li), in nanocarbon materials has always been considered to be one of the most effective methods to improve the optical properties of the system. In this theoretical work, we doped a Li atom to the recently observed all-carboatomic molecule, cyclo[18]carbon (C18), and finally obtained two stable configu...
Preprint
Considering their remarkable chemical stability, the precursors of cyclo[18]carbon (C18), C18-(CO)n (n = 2, 4, and 6), have more practical significance than the elusive C18 ring. In the present paper, the electronic spectrum and (hyper)polarizability of the C18-(CO)n (n = 2, 4, and 6) are studied by theoretical calculations and analyses for reveali...
Article
The evaluation of molecular electrostatic potential (ESP) is a performance bottleneck for many computational chemical tasks like restrained ESP charge fitting or quantum mechanics/molecular mechanics simulations. In this paper, an efficient algorithm for the evaluation of ESP is proposed. It regroups the expression in terms of primitive Gaussian ty...
Article
Planarity is a very important structural character of molecules, which is closely related to many molecular properties. Unfortunately, there is currently no simple, universal, and robust way to measure molecular planarity. In order to fill this evident gap, we propose two metrics of molecular planarity, namely molecular planarity parameter (MPP) an...
Preprint
Full-text available
Although the unique cyclo[18]carbon (C18) realized by recent experiments has been greatly concerned, it has so far remained elusive. In contrast, its precursors C18-(CO)n (n = 6, 4, and 2), which can be separated stably, are of more practical significance. In this paper, the bonding character, electron delocalization, and aromaticity of the C18-(CO...
Preprint
Although the unique cyclo[18]carbon (C18) realized by recent experiments has been greatly concerned, it has so far remained elusive. In contrast, its precursors C18-(CO)n (n = 6, 4, and 2), which can be separated stably, are of more practical significance. In this paper, the bonding character, electron delocalization, and aromaticity of the C18-(CO...
Preprint
Planarity is a very important structural character of molecules, which is closely related to many molecular properties. However, there is currently no simple, universal, and robust way to measure molecular planarity. In order to fill this evident gap, we propose two metrics of molecular planarity, namely molecular planarity parameter (MPP) and span...
Article
The remarkable size dependence of the optical properties of cyclo[2N]carbons (N=3–15) are profoundly explored, and the relevance between aromaticity and optical properties are highlighted. The extrapolation curves fitted for energy level of frontier molecular orbitals, maximum absorption wavelength, and (hyper)polarizability of considered carbon ri...
Preprint
Doping alkali metal atoms, especially lithium (Li), in nanocarbon materials has always been considered as one of the most effective methods to improve the optical properties of the system. In this theoretical work, we doped a Li atom into the recently observed all-carboatomic molecule, cyclo[18]carbon (C<sub>18</sub>), and finally obtained two stab...
Article
Full-text available
Graphically revealing interaction regions in a chemical system enables chemists to quickly recognize where significant interactions have formed. Reduced density gradient (RDG) has already been widely employed in literatures to visually exhibit weak interaction regions, in fact it also has the ability of revealing chemical bonding regions. Unfortuna...
Article
Though density functional theory is widely accepted as one of the most successful developments in theoretical chemistry in the past few decades, the knowledge of how to apply this new electronic structure theory, to help us better understand chemical processes and transformations, is still an unaccomplished task. The information-theoretic approach...
Article
In this article, we present a stand-alone, versatile and flexible code named Shermo for calculating various thermochemistry data. This code is compatible with various mainstream quantum chemistry codes, and has many unique advantages: The output information is very clear and easy to read; thermodynamic quantities can be fully decomposed to contribu...
Article
Recently, Shuhong Xu et al. reported theoretical calculation of molecular structure, bonding, aromaticity, electron delocalization, and electronic spectrum of cyclo[18]carbon in J. Mol. Model., 26, 111 (2020). Due to inappropriate consideration of calculation strategy, misunderstanding of some analysis methods and concepts, and some errors in the d...
Preprint
Graphically revealing interaction regions in a chemical system enables chemists to notice the areas at a glance where significant interactions have formed, it is very helpful in studying chemical bonds, intermolecular and intramolecular interactions. Reduced density gradient (RDG) has already been widely employed in literatures to visually exhibit...
Preprint
Inspired by recent experimental observation of molecular morphology and theoretical predictions of multiple properties of cyclo[18]carbon, we systematically studied photophysical and nonlinear optical properties of cyclo[2 N ]carbons ( N = 3−15) allotropes through density functional theory. This work unveils the unusual optical properties of the sp...
Preprint
p>The photophysical property and optical nonlinearity of an electronic push-pull mesoionic compond, 2-(4-trifluoromethophenyl)-3-methyl-4-(4-methoxyphenyl)-1,3-thiazole-5-thiolate were theoretically investigated with a reliable computing strategy. The essence of the optical properties were then explored through a variety of wave function analysis m...
Article
Cyclo[18]carbon has a very unique geometry and electronic structure. We found that external electric field (EEF) has an ultrastrong regulation effect on various aspects of the cyclo[18]carbon: (1) EEF makes the shape of the cyclo[18]carbon change from a circle to an oval, the elongation is particularly striking at a large EEF magnitude (2) EEF caus...
Article
The theoretical calculations on a direct comparison of hypervalent halogen bonds and conventional halogen bonds have been carried out at the MP2/aug-cc-pVTZ-(PP) level, in which multivalent At center acts as Lewis acid to form a collinear and non-coplanar halogen bond with H 2 O/H 2 S. This series of complexes is defined as hypervalent halogen bond...
Article
The vibrational spectra of cyclo[18]carbon and its analogues, cyclo[2n]carbon (n=3 to 15), were carefully simulated and characterized. The in‐plane C−C stretching vibrations shows strong rigidity, while out‐of‐plane motions seem to be extremely flexible. The solvation effect can enhance signal strengths of the vibrational spectra, but does not evid...
Article
Electrostatics and van der Waals (vdW) interactions are two major components of intermolecular weak interactions. Electrostatic potential has been a very popular function in revealing electrostatic interaction between the system under study and other species, while the role of vdW potential was less recognized and has long been ignored. In this pap...
Article
Recently, an intriguing all-carboatomic ring, cyclo[18]carbon, was observed in the condensed phase for the first time, and it quickly attracted widespread attention. In this article, we first investigated the interaction of the cyclo[18]carbon with external environment through electrostatic potential and our recently proposed van der Waals potentia...
Preprint
Full-text available
Cyclo[18]carbon has a very unique geometry and electronic structure. Based on quantum chemistry calculations, we found that external electric field (EEF) has ultrastrong regulation effect on various aspects of the cyclo[18]carbon. The main findings are as follows: (1) The EEF evidently affects geometric structure of the cyclo[18]carbon, and the rin...
Article
Full-text available
Boron-based materials have been studied extensively due to their potential applications in hydrogen storage and sensing. Doping their surface with transition metals can improve their electronic properties and chemical reactivity. Here, we have studied the titanium-doped boron cluster containing 38 boron atoms using density functional theory, time-d...
Article
Cooperativity effects between a regium-bonding and a pnicogen-bonding interactions in a series of MF···PH3O···MF (M = Cu, Ag, Au) ternary complexes are investigated using theoretical calculations at the MP2/aug-cc-pVTZ(-PP) level. Except for the AuF···PH3O···AuF complex, a pnicogen bond and a regium bond can coexist in each ternary complex. The cal...
Article
Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlin...
Preprint
Full-text available
Calculation of molecular thermodynamic quantities is one of the most frequently involved task in daily quantum chemistry studies. In this article, we present a general, stand-alone, powerful and flexible code named Shermo for calculating various common thermochemistry data. This code is compatible with Gaussian, ORCA, GAMESS-US and NWChem and has m...
Preprint
Electrostatic and van der Waals (vdW) interactions are two major components of intermolecular weak interactions. Electrostatic potential has been a very popular function in revealing electrostatic interaction between the system under study and other species, while the role of vdW potential is less recognized and has long been ignored. In this paper...
Preprint
Full-text available
Electrostatic and van der Waals (vdW) interactions are two major components of intermolecular weak interactions. Electrostatic potential has been a very popular function in revealing electrostatic interaction between the system under study and other species, while the role of vdW potential is less recognized and has long been ignored. In this paper...
Article
cyclo[18]carbon is an all-carboatomic ring observed recently in experiment. Inspired by the distinctive feature in structure and bonding nature, we explored comprehensively its bonding character, electron delocalization, and aromaticity by quantum chemistry calculation and wavefunction analysis. Bond order analysis reveals that this sp-hybridized a...
Article
The electronic spectrum and optical nonlinearity of the sp-hybridized cyclo[18]carbon with novel topology are studied by means of (time-dependent) density functional theory calculations. Molecular orbital analysis shows that the energy levels of σ molecular orbitals of the cyclo[18]carbon are very low, and the energies of two sets of high-lying π m...
Preprint
Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlin...
Article
The unique properties of chemical materials are usually related to the topology and size of their constituent unit. Inspired by a previous report on the synthesis of a separable catenane composed of two Möbius-conjugated nanohoops, we theoretically predicted the optical properties of the Möbius monomer, its Hückel analogue, and some structures deri...
Preprint
Full-text available
Analysis of electronic wavefunction generated by quantum chemistry codes has crucial role in exploring nature of electronic structure and providing valuable information of chemical interest. A file containing wavefunction information is inevitably needed as a communicator between wavefunction analysis codes and quantum chemistry programs. There hav...
Preprint
Analysis of electronic wavefunction generated by quantum chemistry codes has crucial role in exploring nature of electronic structure and providing valuable information of chemical interest. A file containing wavefunction information is inevitably needed as a communicator between wavefunction analysis codes and quantum chemistry programs. There hav...
Article
Benziporphyrins are versatile macrocycles exhibiting aromaticity switching behaviors. The existence of both Hückel and Möbius (anti)aromaticity has been reported in these systems, whose validity is respectively governed by the [4n+2] and [4n] π-electron rule on the macrocyclic pathway. Despite the experimental evidence on the floppiness of benzipor...
Article
Full-text available
The characteristic of π electrons has a crucial role in determining various properties of chemical systems, such as reactivity, aromaticity and spectroscopy. There are a large number of methods could be used for investigating π electronic structure, for example, the well-known electron localization function and multicenter bond order. For completel...
Preprint
Although cyclo[18]carbon has been theoretically and experimentally investigated since long time ago, only very recently it was prepared and directly observed by means of STM/AFM in condensed phase (Kaiser et al., Science , 365 , 1299 (2019)). The unique ring structure and dual 18-center π delocalization feature bring a variety of unusual characteri...
Article
The conversions of photophysical and nonlinear optical (NLO) properties in [32]octaphyrins(1.0.1.0.1.0.1.0) following macrocyclic isomerization between Hückel and Möbius topologies have been studied in detail by means of quantum chemistry calculations. Compared to their quasi-planar analogues, the twisted Möbius and the figure-eight Hückel conforme...
Article
This work studies the underlying nature of H-bonds (HBs) of different types and strengths, and tries to predict binding energies (BEs) based on the properties derived from wavefunction analysis. A total of 42 HB complexes constructed from 28 neutral and 14 charged monomers were considered. This set was designed to sample a wide range of HB strength...
Article
In this work, we report a systematic study on the global and local aromaticity of acenes using a series of model structures from 2-acene to 11-acene. A recently developed ansatz, an information-theoretic approach coached into density functional reactivity theory has been employed, which essentially provides different density functionals characteriz...
Article
A comprehensive investigation of the aromaticity control process of expanded porphyrins was carried out using a variety of visual criteria for the first time. The results show that the indicators based on magnetic property can be used to inspect the global aromaticity of [32]octaphyrins(1.0.1.0.1.0.1.0), while the methods according to electronic (d...
Article
Theoretical researches on the dimers formed by CO with halides of the multivalent astatine as a Lewis-acid center are conducted to examine the typical characteristics of supervalent halogen bond. Calculation on MP2/aug-cc-pVTZ level reveals that the multiple nucleophilic sites of multivalent halide monomers can promote the formation of various type...
Article
It is well-known that the kinetic energy density (KED) functional is the most difficult to approximate in density functional theory (DFT), yet to take full advantage of DFT with its density-based descriptive capability of molecular properties, an accurate account of KED is a must. To have a better idea of how an approximate KED formula behaves and...
Article
Regium bonds interaction between phosphine oxide (H3PO), the trans phosphinuous acid (T-PH2OH), the cis phosphinuous acid (C-PH2OH) and MX (M═Cu, Ag, Au; X═F, Cl, Br) complexes were investigated by means of ab initio MP2/aug-cc-pVTZ method. For phosphinuous acid and MX complexes, two types of regium bonded interaction (trans and cis complexes) are...
Article
Full-text available
Originated from the cyclic delocalization of electrons resulting in extra stability and instability, aromaticity and antiaromaticity are important chemical concepts whose appreciation and quantification are still much of recent interest in the literature. Employing information-theoretic quantities can provide us with more insights and better unders...
Article
The bonding mechanisms between DEHP, PFOS, butylparaben and benzo[a]pyrene with the DNA were recently published [1] and showed intriguing mechanisms of complex formation between these priority pollutants and the gene core fragment of the p53 suppressor which were analyzed at the electronic level. The study supplied also important bonding data, incl...
Article
Very recently [J. Phys. Chem. A 2018, 122 (11), 3087–3095], we proposed to employ the Pauli energy to identify and determine strong covalent interactions (SCI), whose bond order are equal to or larger than two. This is done through the signature isosurface shape between the two bonding atoms. We discovered that the signature shape for a double, tri...
Article
Intermolecular interaction of XH2P···MY (X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes was investigated by means of an ab initio method. The molecular interaction energies are in the order Ag < Cu < Au and increased with the decrease of RP···M. Interaction energies are strengthened when electron-donating substituents X connect...
Article
Although a large variety of aromatic systems have been unveiled in the literature, justifying their origin of stability and understanding their nature of aromaticity is still an unaccomplished task. In this work, using tools recently developed by us within the density functional reactivity theory framework, where we employ simple density functional...
Article
As one of the most widely used chemical concepts whose origin can be traced back to Lewis theory of bonding a century ago, a covalent bond involves sharing one or more pairs of electrons between atoms. A strong covalent interaction (SCI) is such a covalent bond that two or more electron pairs are shared, yielding a double, triple, quadruple or even...
Article
The [3+2] cycloaddition (32CA) reaction between trifluoroacetonitrile N-oxide (NO 7) and 2,2,4,4-tetramethyl-3-thioxocyclobutan-1-one (THK 12) as well as the self-dimerization of NO 7 as a competitive pathway were studied within the Molecular Electron Density Theory (MEDT) using several DFT functionals together with def2-TZVP basis set. Taking CCSD...
Article
Full-text available
Numerous real space functions have been purposed so far for unveiling chemically interesting molecular electronic structure characteristics, such as chemical bonds, lone pairs, and multicenter electronic conjugations. Among these analysis methods, electron localization function (ELF), Laplacian of electron density (∇2ρ), and deformation density (ρd...
Article
Steric effect is one of the most widely used chemical concepts in chemistry, yet a generally accepted implementation of its formulation and quantification on the basis a theoretical viewpoint, if...
Article
Corannulene is an interesting yet special molecule, which has witnessed widespread applications. It is aromatic, but not planar and the total number of 20 π electrons is in conflict with Hückel's 4n + 2 rule. In this work, we design a series of analogous model systems based on this molecule with the central ring size extended from five members to t...
Article
Molecular acidity is one of the important physiochemical properties of a molecular system, yet its accurate calculation and prediction are still an unresolved problem in the literature. In this work, we propose to make use of the quantities from the information-theoretic (IT) approach in density functional reactivity theory and provide an accurate...
Article
The nature and origin of the generalized anomeric effect is investigated with energy components and information-theoretic quantities from density functional reactivity theory. Forty-five systems with the general formula of R1-X-CH2-Y-R2 were examined, where R1 and R2 are functional groups and X and Y as electronegative heteroatoms. Our results show...
Article
The MP2 ab initio quantum chemistry methods were utilized to study the halogen-bond and pnicogen-bond system formed between PH2X (X = Br, CH3, OH, CN, NO2, CF3) and BrY (Y = Br, Cl, F). Calculated results show that all substituent can form halogen-bond complexes while part substituent can form pnicogen-bond complexes. Traditional, chlorine-shared a...
Article
Even though the concept of aromaticity and antiaromaticity is extremely important and widely used, there still exist lots of controversies in the literature, which are believed to be originated from the fact that there are so many aromatic types discovered and at the same time there are many aromaticity indexes proposed. In this work, using seven s...
Article
In this work, we apply the quantities from the information-theoretic approach in density functional reactivity theory to examine the origin and nature of the anomeric effect, which is the preference of heteroatomic substituents within the cyclohexane ring to be in the axial orientation rather than the sterically less hindered equatorial position. U...
Article
In this work, we designed a series of superalkali-doped Si12 C12 nanocage M3 O@Si12 C12 (M = Li, Na, K) with donor-acceptor framework. Density functional theory calculations demonstrated that the HOMO-LUMO gap of the complexes conspicuously narrowed with increase of atomic number of the alkali metal, the value decreased from 5.452 eV of pure Si12 C...
Article
One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a...
Article
How to accurately predict electronic properties of a Columbic system with the electron density obtained from experiments such as X-ray crystallography is still an unresolved problem. The information-theoretic approach recently developed in the framework of density functional reactivity theory is one of the efforts to address the issue. In this work...
Article
Full-text available
Charge decomposition analysis (CDA) is an important method to study charge transfer problems in depths. In this paper, we introduced CDA method, elucidated the issues that needed attention in the calculation, and presented a new form of CDA, which was called GCDA. At HF and DFT levels, GCDA is equivalent to CDA, while GCDA is more applicable at pos...
Article
Full-text available
Predicting the reactivity of nucleophilic reaction at different sites has important theoretical and practical significance. Many prediction methods solely based on the electronic structure of reactants have been proposed. In this paper, detailed comparative analyses on the reliability of 14 methods are carried out and three series of molecules, car...