Relaxation Paths Research Articles

Photocyclization and Photoisomerization Mechanisms of an Indolylfulgide Derivative in Acetonitrile Solution by Using the QM (MS-CASPT2)/MM Method.

The indolylfulgide systems have been extensively investigated due to their potential applications as photochromic materials. In this work, the photoinduced ring-closure/opening and isomerization reactions of a photochromic indolylfulgide in vacuum and acetonitrile solvent have been investigated by means of MS-CASPT2//CASSCF and QM(MS-CASPT2)//CASSCF/MM. The deactivation mechanisms of indolylfulgide have been proposed based on the optimized structures in the S0 and S1 states, S1/S0 conical intersections, and the calculated minimum-energy paths. After excitation into the first singlet excited-state, which is spectroscopically bright in the Franck-Condon point of the E, the photoprocesses proceed toward a nearby S1 minimum. Then, two possible nonadiabatic relaxation paths exist to repopulate the ground state. In the ring closure reaction, the S1 E isomer evolves directly into one S1/S0 conical intersection and decays to the ground state with bifurcation toward C or E. In the E → Z tautomerization pathway, the excited system can deactivate to the S0 state via a distinct conical intersection. The minimum-energy paths of the indolylfulgide revealed that the ring closure reaction in the solvent is more facile to take place than the E → Z isomerization after irradiation of the same E. Furthermore, for the ring opening reaction from the C side, there exists an energy barrier (11.1 kcal/mol) in the S1 state before arriving at the conical intersection. The computational results showed that the solvent has some influence on the system compared with that in the gas phase. The present work could contribute to comprehending the photoreactions of indolylfulgide and its derivatives in solution.

Effect of Pyrrolidinedithiocarbamate Ligand on the Luminescence Properties of Heteroligand Samarium and Europium Complexes: Experimental and Theoretical Study.

The photophysical properties of two isostructural heteroligand lanthanide complexes of general formula Ln(pdtc)3(phen) (pdtc = pyrrolidinedithiocarbamate anion, phen = 1,10-phenanthroline), Ln = Sm3+ (1), Eu3+ (2)) were studied in solid state and dichloromethane (DCM) solution. The two lanthanide complexes were investigated by experimental techniques for structural (single-crystal X-ray diffraction analysis of 1, powder XRD, TG-DTA) and spectroscopic [electron paramagnetic resonance (EPR), infrared (IR), ultraviolet-visible (UV-vis), photoluminescence (PL)] characterization. DFT/TDDFT/ωB97xD and multireference SA-CASSCF/NEVPT2 calculations with perturbative spin-orbit coupling corrections were applied to construct the Jablonski energy diagrams and to discuss the excited state energy transfer mechanism with competing excited state processes and possible sensitized mechanism of metal-centered emission. The first excited state (S1) involved in the excited state energy transfer L(antenna)-to-Ln was predicted to have interligand (pdtc-to-phen) charge transfer character in contrast to the previously predicted ligand-to-metal charge transfer character. The theoretical consideration showed similar relaxation paths and luminescence quenching channels and appropriate Donor*(phen)-Acceptor*(Ln3+) energy gap for 1 and 2. The experimental measurements in the solid state, however, showed efficient luminescence and good ability to convert UV to visible light only for the Sm(pdtc)3(phen) complex. The minor emission of 2 was explained by partial reduction of Eu3+, confirmed by EPR and calculated electron density distribution data.

Considerations on the relaxation time in shear-driven jamming.

We study the jamming transition in a model of elastic particles under shear at zero temperature, with a focus on the relaxation time τ_{1}. This relaxation time is from two-step simulations where the first step is the ordinary shearing simulation and the second step is the relaxation of the energy after stopping the shearing. τ_{1} is determined from the final exponential decay of the energy. Such relaxations are done with many different starting configurations generated by a long shearing simulation in which the shear variable γ slowly increases. We study the correlations of both τ_{1}, determined from the decay, and the pressure, p_{1}, from the starting configurations as a function of the difference in γ. We find that the correlations of p_{1} are longer lived than the ones of τ_{1} and find that the reason for this is that the individual τ_{1} is controlled both by p_{1} of the starting configuration and a random contribution which depends on the relaxation path length-the average distance moved by the particles during the relaxation. We further conclude that it is γ_{τ}, determined from the correlations of τ_{1}, which is the relevant one when the aim is to generate data that may be used for determining the critical exponent that characterizes the jamming transition.

Ultrafast photochemistry and electron-diffraction spectra in n → (3s) Rydberg excited cyclobutanone resolved at the multireference perturbative level.

We study the ultrafast time evolution of cyclobutanone excited to the singlet n → Rydberg state through non-adiabatic surface-hopping simulationsperformed at extended multi-state complete active space second-order perturbation (XMS-CASPT2) level of theory. These dynamics predict relaxation to the ground-state with a timescale of 822 ± 45fs with minimal involvement of the triplets. The major relaxation path to the ground-state involves a three-state degeneracy region and leads to a variety of fragmented photoproducts. We simulate the resulting time-resolved electron-diffraction spectra, which track the relaxation of the excited state and the formation of various photoproducts in the ground state.

A review on dynamics of permeability-glycoprotein in efflux of chemotherapeutic drugs

Permeability-glycoprotein (P-gp) belongs to the ABS transporter protein family, with a high expression rate in cancerous cells. The substrate/inhibitors of the protein are structurally diverse, with no lucid mechanism of inhibition. There are two schools of thought on the inhibition mechanism: (i) P-gp inhibitors bind to the huge hydrophobic cavity between two Trans-Membrane Domains (TMDs), supported by ample literary proof and (ii) P-gp inhibitors bind to the vicinity of Nucleotide-Binding Sites (NBSs). Structural biologists have presented several experimental and theoretical structures of P-gp with bound nucleotides and inhibitors to explain the same. However, the available experimental P-gp structures are insufficient to address the catalytic transition path of mammalian P-gp in detail, thus the dynamics and mechanism by which drugs are effluxed is still unknown. Targeted Molecular Dynamics (targeted MD) could be used to minutely analyse and explore the catalytic transition inward open (IO) to outward open (OO) and relaxation path (OO to IO). Finally, analysis of targeted MD trajectory may help to explore different conformational states of Pg-p (reaction coordinate of catalytic transition/relaxation), efflux of compounds aided by the dynamics of Nucleotide Binding Domains/NBDs (ATP coupled process) and TMDs (peristalsis-like movement pushes the bound molecule). This review presents an understanding of the catalytic transition and dynamics of protein which provides insights at the efflux of chemotherapeutic drug using in cancer treatment.

Inferring nonequilibrium thermodynamics from tilted equilibrium using information-geometric Legendre transform

Nonstationary thermodynamic quantities depend on the full details of nonstationary probability distributions, making them difficult to measure directly in experiments and numerics. We propose a method to infer thermodynamic quantities in relaxation processes by measuring only a few observables, using additional information obtained from measurements in tilted equilibrium, i.e., equilibrium with external fields applied. Our method is applicable to arbitrary classical stochastic systems, possibly underdamped, that relax to equilibrium. The method allows us to compute the exact value of the minimum entropy production (EP) compatible with the nonstationary observations, giving a tight lower bound on the true EP. Under a certain additional condition, it also allows the inference of the EP rate, thermodynamic forces, and a constraint on relaxation paths. Our method uses a Legendre transform of EP at the level of probability distributions, which we develop based on a similar Legendre transform in information geometry. Published by the American Physical Society 2024

Vibrational anharmonicity of A-band related optical center and its temperature dependence studied by femtosecond laser excitation in bulk natural diamond

Unusual A-band spectra with well-resolved quasi-periodical phonon progressions of multiple peaks (N\(\sim \)9) were excited in a natural diamond by 515-nm, 300-fs laser pulses at variable pre-heating temperatures of 24-200oC. The non-radiative multi-phonon part of the relaxation path was comparable with the total relaxation energy (zero-phonon line energy), pointing out some extended defects (e.g., dislocations) as the recombination center of the A-band emission. The derived temperature dependences of the peak intensities, separations and half-widths of the separate spectral peaks in the A-band phonon progressions indicate the different trends for vibration-free zero-phonon transition and vibration-related lower-energy transitions to high vibrational levels of the bottom state – lower thermal damping and more softened phonon for the zero-phonon transition, also implying the extended defect origin of the A-band photoluminescence.

Modulation of lanthanide luminescence by carbamoylmethylphosphine oxide ligand: A theoretical study

The antenna capacity of Phenacyldiphenylphosphine oxide (Phenac), combining C=O and P=O donor groups was established by theoretical examination of its chromophore properties, binding ability to encapsulate and stabilize lanthanide complexes and potential to sensitize the EuIII and TbIII luminescence in Eu(Phenac)2(NO3)3(H2O) (1), Eu(Phenac)2(NO3)3 (2), Eu(Phenac)3(NO3)3 (3) and Tb(Phenac)2(NO3)3(H2O) (4) complexes in vacuum, solution and solid phase. The ligand-centered singlet and triplet excited state energies, the rates and lifetimes for the rival nonradiative (S1→T1,2 intersystem crossing (ISC)) and radiative and nonradiative S1→S0 and T1→S0 relaxation were predicted by means of DFT/TDDFT/ωB97XD calculations. Similar relaxation paths were found for all complexes. The absorbed energy by Sn > 1(π-π*) states relaxed to T1min by major ISC mechanism S1→T2→T1. The long radiative lifetime of S1→S0 due to n(p(C)(O))π-π*,p(P) character facilitated the forward ISC process. The environment, Phenac's number and LnIII size affect the T1 energy ∼0.1 eV. The calculated (Phenac→EuIII) energy transfer rates suggested the most likely T1 → 5D1/5D0 channels for a population of emitting metal-centered states. The small Φ of EuIII and larger luminescence of TbIII were discussed and explained. The importance of the P=O and C=O groups for the coordination ability and absorption properties of Phenac has been elucidated.

Quantitative Mapping of Transient Thermodynamic States in Ultrafast Laser Nanostructuring of Quartz

Understanding material structural reaction to light is of utmost importance to advance processing resolution in ultrafast laser volume structuring into the nanoscale. Selective thermodynamic pathways are required to quench energy transport in the most rapid manner and to confine the process to nanometer lengths, bypassing optical resolution. Quantifying material dynamics under confinement, with in situ access to transient local temperature and density parameters, thus becomes key in understanding the process. We report in situ reconstruction of thermodynamic states over the entire matter relaxation path in bulk α -quartz irradiated by ultrafast nondiffractive laser beams using time-resolved qualitative and quantitative optical phase microscopy. Thermooptic dynamics indicate rapid spatially confined crystalline-to-amorphous transition to a hot dense fused silica form. Densification exceeds 20% and the matrix temperature rises to more than 2,000 K in the first nanosecond. This structural state relaxes in hundreds of nanoseconds. The dispersion and time design of the optical beam to picosecond durations increases the spatial confinement and triggers an extreme nanostructuring process based on nanocavitation that occurs within the amorphizing material, where the low-viscosity phase lowers the mechanical requirements for the process. Processing feature scales of less than a tenth of the optical wavelength are obtained in the volume. This allows for structural and morphological nanoscale material features under 3D confinement that can engineer optical materials.

Host-Guest-Interaction Enhanced Nitric Oxide Photo-Generation within a Pillar[5]arene Cavity for Antibacterial Gas Therapy.

Supramolecular macrocycles with intrinsic cavities have been widely explored as containers to fabricate versatile functional materials via specific host-guest recognitions. However, relatively few studies have focused on the modulation of guest reactivity within a macrocyclic cavity. Here, we demonstrate the confinement effect of pillar[5]arene with an electron-rich and precise cavity that can dramatically enhance guest photoactivity and nitric oxide (NO) generation upon visible light irradiation. Mechanism studies reveal that it is achieved through increasing the ground state nitro-aromatic torsion angle, suppressing the intersystem crossing relaxation path of the S1 state, and accelerating the isomerization reaction path of guest molecules. This NO-generating system displays broad-spectrum antibacterial, biofilm inhibition, and dispersal activities. Moreover, it can accelerate the healing of methicillin-resistant Staphylococcus aureus (MRSA)-infected wounds in vivo.

Theoretical studies on the photo protective mechanism of curcuminoids

In this work, the deactivation pathways of curcuminoids after photoexcitation was studied by employing density functional theory to explore their UVA radiation screening capacity. A comprehensive computational characterization of the excited-state processes of curcumin, demethoxycurcumin, and bis-demethoxycurcumin was done. The molecules exist in diketo and enol forms which are in equilibrium and interconvertible through keto-enol tautomerism. The enolic forms of each of the studied molecules have eight geometric cis–trans isomers as a result of torsion rotation about three different carbon–carbon double bonds across the aliphatic chain. For each geometric isomer, sixteen possible rotamers are found to exist due to rotation about five different carbon–carbon single bond rotations, also across the skeleton of the aliphatic chain. Upon photoexcitation, the studied molecules follow three main pathways of radiationless decay: (a) rotamerism and interconversion between rotamers of comparable energies which are in equilibrium, (b) interconversion between the cis–trans geometrical isomers where an efficient vibrational relaxation path is formed at ∼90° during torsion rotation about carbon–carbon double bond, and (c) excited state intramolecular proton transfer in a single O–H stretching vibration through a cyclic intramolecular hydrogen bonded ring formed at the centre of the molecule giving back the original structure. The absorption and emission spectra of the molecules were also simulated where the theoretically obtained absorption and emission maxima are close to the reported experimental values.

Application of Boltzmann kinetic equations to model X-ray-created warm dense matter and plasma.

In this review, we describe the application of Boltzmann kinetic equations for modelling warm dense matter and plasma formed after irradiation of solid materials with intense femtosecond X-ray pulses. Classical Boltzmann kinetic equations are derived from the reduced N-particle Liouville equations. They include only single-particle densities of ions and free electrons present in the sample. The first version of the Boltzmann kinetic equation solver was completed in 2006. It could model non-equilibrium evolution of X-ray-irradiated finite-size atomic systems. In 2016, the code was adapted to study plasma created from X-ray-irradiated materials. Additional extension of the code was then also performed, enabling simulations in the hard X-ray irradiation regime. In order to avoid treatment of a very high number of active atomic configurations involved in the excitation and relaxation of X-ray-irradiated materials, an approach called 'predominant excitation and relaxation path' (PERP) was introduced. It limited the number of active atomic configurations by following the sample evolution only along most PERPs. The performance of the Boltzmann code is illustrated in the examples of X-ray-heated solid carbon and gold. Actual model limitations and further model developments are discussed. This article is part of the theme issue 'Dynamic and transient processes in warm dense matter'.

Benchmark Structures and Conformational Landscapes of Amino Acids in the Gas Phase: A Joint Venture of Machine Learning, Quantum Chemistry, and Rotational Spectroscopy.

The accurate characterization of prototypical bricks of life can strongly benefit from the integration of high resolution spectroscopy and quantum mechanical computations. We have selected a number of representative amino acids (glycine, alanine, serine, cysteine, threonine, aspartic acid and asparagine) to validate a new computational setup rooted in quantum-chemical computations of increasing accuracy guided by machine learning tools. Together with low-lying energy minima, the barriers ruling their interconversion are evaluated in order to unravel possible fast relaxation paths. Vibrational and thermal effects are also included in order to estimate relative free energies at the temperature of interest in the experiment. The spectroscopic parameters of all the most stable conformers predicted by this computational strategy, which do not have low-energy relaxation paths available, closely match those of the species detected in microwave experiments. Together with their intrinsic interest, these accurate results represent ideal benchmarks for more approximate methods.

Intermolecular-Type Conical Intersections in Benzene Dimer.

The equilibrium and conical intersection geometries of the benzene dimer were computed in the framework of the conventional, linear-response time-dependent and spin-flipped time-dependent density functional theories (known as DFT, TDDFT and SF-TDDFT) as well as using the multiconfigurational complete active space self-consistent field (CASSCF) method considering the minimally augmented def2-TZVPP and the 6-31G(d,p) basis sets. It was found that the stacking distance between the benzene monomers decreases by about 0.5 Å in the first electronic excited state, due to the stronger intermolecular interaction energy, bringing the two monomers closer together. Intermolecular-type conical intersection (CI) geometries can be formed between the two benzene molecules, when (i) both monomer rings show planar deformation and (ii) weaker (approximately 1.6-1.8 Å long) C-C bonds are formed between the two monomers, with parallel and antiparallel orientation with respect to the monomer. These intermolecular-type CIs look energetically more favorable than dimeric CIs containing only one deformed monomer. The validity of the dimer-type CI geometries obtained by SF-TDDFT was confirmed by the CASSCF method. The nudged elastic band method used for finding the optimal relaxation path has confirmed both the accessibility of these intermolecular-type CIs and the possibility of the radiationless deactivation of the electronic excited states through these CI geometries. Although not as energetically favorable as the previous two CI geometries, there are other CI geometries characterized by the relative rotation of monomers at different angles around a vertical C-C axis.

Structural and optical investigation of novel Sr1-xNa2xZrO3 perovskite nanoparticles

Novel Sr1−xNa2xZrO3 (0 ≤ x ≤ 0.4) perovskite nanoparticles have been fabricated via the citrate-ethylene glycol sol-gel route and systemically studied. The XRD analysis shows Sr1−xNa2xZrO3 crystallized in orthorhombic structure, Rietveld refinement analysis revealed that Na ion acts positively to prevent large distortion of the perovskite, with a cell-volume contraction compared to the pure SrZrO3. Raman spectral results confirmed the existence of minor impurities. Besides, the calculated low phonon energy of 442 cm−1 makes Sr1−xNa2xZrO3 perovskite a promising host matrix for phosphor-based photonic applications. The decrease in the optical band gap (Egap) from 4.85 eV to 4.42 eV is link to the formation of localized states in the band gap due to lattice disorder and oxygen vacancies. Photoluminescence results revealed broad band emissions in the range 300–800 nm as a result of transitions involving multiple relaxation paths. The Sr1−xNa2xZrO3 perovskite is a promising candidate for phosphor host matrix.

Nuclear dipolar relaxation induced by interacting ground state electron spins

In samples used for dynamic nuclear polarization (DNP), spin–lattice relaxation times are usefully increased by going to high magnetic field and low temperature, typically several tesla and below 1 K. But the relaxation times for dipolar components of the nuclear spin energy remain stubbornly shorter than those for the Zeeman energy: dipolar order decays faster than the polarization itself by a huge factor—up to four orders of magnitude or more in the materials studied thus far. Such fast nuclear dipolar relaxation poses experimental challenges, for instance, when transferring polarization between different nuclear spin species via intermediate nuclear order: a proven technique to polarize rare nuclear spins. The origin of this fast nuclear dipolar relaxation remained a mystery for a long time—existing theories of nuclear spin–lattice relaxation could at best predict about one order of magnitude difference between the nuclear dipolar and nuclear Zeeman relaxation rates—until it was recently discovered to be due to conversion of nuclear dipolar energy into super-hyperfine energy induced by nuclear flip-flop transitions. A previous article showed that the inclusion of this relaxation path enables a quantitative explanation of nuclear dipolar relaxation induced by photo-excited triplet states. This article extends the theory to nuclear dipolar relaxation induced by ground state electron spins and demonstrates that this new mechanism enables a precise quantitative prediction from first principles of the nuclear dipolar relaxation rate for Ca(OH)2 doped with O2- centres—in which DNP is caused by the solid effect (SE)—and LiF doped with F-centres—in which DNP is caused by thermal mixing (TM)—both at 5.5 T and 0.4 K. It is noticed that the proposed mechanism extends to other spin systems which has implications for e.g. TM and spectral diffusion.

Interesting chemical and physical features of the products of the reactions between trivalent lanthanoids and a tetradentate Schiff base derived from cyclohexane-1,2-diamine.

The initial use of a tetradentate Schiff base (LH2) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO3)3·xH2O (Ln = lanthanoid or yttrium) and LH2 in MeOH/CH2Cl2 has provided access to isostructural complexes [Ln(NO3)3(L'H2)(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L'H2 possessing six aliphatic -CH2- groups instead of the -CH-(CH2)4-CH- unit of the cyclohexane ring, i.e. an unusual ring-opening of the latter has occurred. A mechanism for this LnIII-assisted/promoted LH2 → L'H2 transformation has been proposed assuming transient LnII species and a second LH2 molecule as the H2 source for the reduction of the cyclohexane moiety. DFT calculations provide strong evidence for the great thermodynamic stability of the products in comparison with analogous complexes containing the original intact ligand. The structures of the PrIII, SmIII, GdIII, TbIII, and HoIII complexes have been determined by single-crystal X-ray crystallography. The 9-coordinate LnIII centre in the molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the bidentate chelating organic ligand, and one oxygen atom from the coordinated MeOH group. In the overall neutral bis(zwitterionic) L'H2 ligand, the acidic H atoms are clearly located on the imino nitrogen atoms and this results in the formation of an unusual 16-membered chelating ring. The coordination polyhedra defined by the nine donor atoms around the 4f-metal-ion centres can be best described as distorted, spherical capped square antiprisms. The EuIII, TbIII, and DyIII complexes exhibit LnIII-based luminescence in the visible region, with the coordinated L'H2 molecule acting as the antenna. Ac magnetometry experiments show that the DyIII member of the family behaves as an SIM at zero field and under external dc fields of 0.1 and 0.2 T without the enhancement of the peaks' maxima, suggesting that QTM is not the relaxation path. The GdIII complex behaves, rather unexpectedly, as a SIM with two different magnetic relaxation paths occurring at very close temperatures; this behaviour is tentatively attributed to a very small axial zero-field splitting (D ∼ 0.1 cm-1), which cannot be detected by magnetization or susceptibility experiments. The prospects of the present, first results in the lanthanoid(III)-LH2 chemistry are discussed.

Ultrafast photoisomerization mechanism of azaborine revealed by nonadiabatic molecular dynamics simulations.

1,2-Dihydro-1,2-azaborine is an isoelectronic analog of benzene with a B-N substitution, and its unique photoisomerization behavior, which is distinct from that of benzene, has drawn significant attention. To understand the detailed mechanism of azaborine photochemistry considering the dynamical effect and gain a comprehensive understanding of photochemical reactions, we investigated the photoisomerization dynamics of azaborine using nonadiabatic molecular dynamics simulations with Tully's surface hopping algorithm. Herein, the structural and energetic analyses of the trajectories revealed three different paths: direct relaxation (path 1), relaxation via a prefulvene-like intermediate (path 2), and formation of the Dewar isomer as a photoproduct (path 3). Our results confirmed that the photoisomerization of azaborine follows the energetically favored pathway predicted by the previous minimum energy path (MEP) calculations, exclusively forming the Dewar isomer, which is consistent with the experimental observations. Additionally, despite the low quantum yield found in our simulations, the high-level excitation energy calculations support the complete conversion observed in the experiments.

Transition state search and geometry relaxation throughout chemical compound space with quantum machine learning.

We use energies and forces predicted within response operator based quantum machine learning (OQML) to perform geometry optimization and transition state search calculations with legacy optimizers but without the need for subsequent re-optimization with quantum chemistry methods. For randomly sampled initial coordinates of small organic query molecules, we report systematic improvement of equilibrium and transition state geometry output as training set sizes increase. Out-of-sample SN2 reactant complexes and transition state geometries have been predicted using the LBFGS and the QST2 algorithms with an root-mean-square deviation (RMSD) of 0.16 and 0.4 Å-after training on up to 200 reactant complex relaxations and transition state search trajectories from the QMrxn20 dataset, respectively. For geometry optimizations, we have also considered relaxation paths up to 5'595 constitutional isomers with sum formula C7H10O2 from the QM9-database. Using the resulting OQML models with an LBFGS optimizer reproduces the minimum geometry with an RMSD of 0.14 Å, only using ∼6000 training points obtained from normal mode sampling along the optimization paths of the training compounds without the need for active learning. For converged equilibrium and transition state geometries, subsequent vibrational normal mode frequency analysis indicates deviation from MP2 reference results by on average 14 and 26 cm-1, respectively. While the numerical cost for OQML predictions is negligible in comparison to density functional theory or MP2, the number of steps until convergence is typically larger in either case. The success rate for reaching convergence, however, improves systematically with training set size, underscoring OQML's potential for universal applicability.

A three-stage network DEA approach for performance evaluation of BIM application in construction projects

BIM application in the construction industry is still low in China, mainly due to the lack of effective measures for BIM application evaluation. Therefore, this study takes BIM application as the research object to propose a three-stage network DEA approach for performance evaluation. The BIM application performance evaluation indicators are determined based on the balanced scorecard method and Delphi method, and a three-stage network DEA model is established to optimize the BIM application performance. The three-stage network DEA model established in this study can solve the problem that the traditional DEA model treats the internal structure as a “black box”. The model is then applied to the actual case of 9 construction projects, including relaxation value analysis and path optimization, to identify the critical path for the reallocation of resources. This paper studies the performance evaluation of BIM application, which is conducive to the further improvement of the theory of BIM management, and also can effectively improve the performance of construction projects and bring practical benefits to construction enterprises.