Direct Random Phase Approximation Research Articles

Contributions beyond direct random-phase approximation in the binding energy of solid ethane, ethylene, and acetylene

The random-phase approximation (RPA) includes a subset of higher than second-order correlation-energy contributions, but stays in the same complexity class as the second-order Møller–Plesset perturbation theory (MP2) in both Gaussian-orbital and plane-wave codes. This makes RPA a promising ab initio electronic structure approach for the binding energies of molecular crystals. Still, some issues stand out in practical applications of RPA. Notably, compact clusters of nonpolar molecules are poorly described, and the interaction energies strongly depend on the reference single-determinant state. Using the many-body expansion of the binding energy of a crystal, we investigate those issues and the effect of beyond-RPA corrections. We find the beneficial effect of quartic-scaling exchange and non-ring coupled-cluster doubles corrections. The nonadditive interactions in compact trimers of molecules are improved by using the self-consistent Hartree–Fock orbitals instead of the usual Kohn–Sham states, but this kind of orbital input also leads to underestimated dimer energies. Overall, a substantial improvement over the RPA with a renormalized singles approach is possible at a modest quartic-scaling cost, which encourages further research into additional RPA corrections.

Corrected density functional theory and the random phase approximation: Improved accuracy at little extra cost.

We recently introduced an efficient methodology to perform density-corrected Hartree-Fock density functional theory [DC(HF)-DFT] calculations and an extension to it we called "corrected" HF DFT [C(HF)-DFT] [Graf and Thom, J. Chem. Theory Comput. 19 5427-5438 (2023)]. In this work, we take a further step and combine C(HF)-DFT, augmented with a straightforward orbital energy correction, with the random phase approximation (RPA). We refer to the resulting methodology as corrected HF RPA [C(HF)-RPA]. We evaluate the proposed methodology across various RPA methods: direct RPA (dRPA), RPA with an approximate exchange kernel, and RPA with second-order screened exchange. C(HF)-dRPA demonstrates very promising performance; for RPA with exchange methods, on the other hand, we often find over-corrections.

Analytical Second-Order Properties for the Random Phase Approximation: Nuclear Magnetic Resonance Shieldings.

A method for the analytical computation of nuclear magnetic resonance (NMR) shieldings within the direct random phase approximation (RPA) is presented. As a starting point, we use the RPA ground-state energy expression within the resolution-of-the-identity approximation in the atomic-orbital formalism. As has been shown in a recent benchmark study using numerical second derivatives [Glasbrenner, M. J. Chem. Theory Comput. 2022, 18, 192], RPA based on a Hartree-Fock reference shows accuracies comparable to coupled cluster singles and doubles (CCSD) for NMR chemical shieldings. Together with the much lower computational cost of RPA, it has emerged as an accurate method for the computation of NMR shieldings. Therefore, we aim to extend the applicability of RPA NMR to larger systems by introducing analytical second-order derivatives, making it a viable method for the accurate and efficient computation of NMR chemical shieldings.

Sparse tensor based nuclear gradients for periodic Hartree-Fock and low-scaling correlated wave function methods in the CP2K software package: A massively parallel and GPU accelerated implementation.

The development of novel double-hybrid density functionals offers new levels of accuracy and is leading to fresh insights into the fundamental properties of matter. Hartree-Fock exact exchange and correlated wave function methods, such as second-order Møller-Plesset (MP2) and direct random phase approximation (dRPA), are usually required to build such functionals. Their high computational cost is a concern, and their application to large and periodic systems is, therefore, limited. In this work, low-scaling methods for Hartree-Fock exchange (HFX), SOS-MP2, and direct RPA energy gradients are developed and implemented in the CP2K software package. The use of the resolution-of-the-identity approximation with a short range metric and atom-centered basis functions leads to sparsity, allowing for sparse tensor contractions to take place. These operations are efficiently performed with the newly developed Distributed Block-sparse Tensors (DBT) and Distributed Block-sparse Matrices (DBM) libraries, which scale to hundreds of graphics processing unit (GPU) nodes. The resulting methods, resolution-of-the-identity (RI)-HFX, SOS-MP2, and dRPA, were benchmarked on large supercomputers. They exhibit favorable sub-cubic scaling with system size, good strong scaling performance, and GPU acceleration up to a factor of 3. These developments will allow for double-hybrid level calculations of large and periodic condensed phase systems to take place on a more regular basis.

Toward Pair Atomic Density Fitting for Correlation Energies with Benchmark Accuracy.

Pair atomic density fitting (PADF) has been identified as a promising strategy to reduce the scaling with system size of quantum chemical methods for the calculation of the correlation energy like the direct random-phase approximation (RPA) or second-order Møller-Plesset perturbation theory (MP2). PADF can however introduce large errors in correlation energies as the two-electron interaction energy is not guaranteed to be bounded from below. This issue can be partially alleviated by using very large fit sets, but this comes at the price of reduced efficiency and having to deal with near-linear dependencies in the fit set. One posibility is to use global density fitting (DF), but in this work, we introduce an alternative methodology to overcome this problem that preserves the intrinsically favorable scaling of PADF. We first regularize the Fock matrix by projecting out parts of the basis set which gives rise to orbital products that are hard to describe by PADF. After having thus obtained a reliable self-consistent field solution, we then also apply this projector to the orbital coefficient matrix to improve the precision of PADF-MP2 and PADF-RPA. We systematically assess the accuracy of this new approach in a numerical atomic orbital framework using Slater type orbitals (STO) and correlation consistent Gaussian type basis sets up to quintuple-ζ quality for systems with more than 200 atoms. For the small and medium systems in the S66 database we show the maximum deviation of PADF-MP2 and PADF-RPA relative correlation energies to DF-MP2 and DF-RPA reference results to be 0.07 and 0.14 kcal/mol, respectively. When the new projector method is used, the errors only slightly increase for large molecules and also when moderately sized fit sets are used the resulting errors are well under control. Finally, we demonstrate the computational efficiency of our algorithm by calculating the interaction energies of large, non-covalently bound complexes with more than 1000 atoms and 20000 atomic orbitals at the RPA@PBE/CC-pVTZ level of theory.

Performance of Localized-Orbital Coupled-Cluster Approaches for the Conformational Energies of Longer n-Alkane Chains.

We report an update and enhancement of the ACONFL (conformer energies of large alkanes [J. Phys. Chem. A2022,126, 3521-3535]) dataset. For the ACONF12 (n-dodecane) subset, we report basis set limit canonical coupled-cluster with singles, doubles, and perturbative triples [i.e., CCSD(T)] reference data obtained from the MP2-F12/cc-pV{T,Q}Z-F12 extrapolation, [CCSD(F12*)-MP2-F12]/aug-cc-pVTZ-F12, and a (T) correction from conventional CCSD(T)/aug-cc-pV{D,T}Z calculations. Then, we explored the performance of a variety of single and composite localized-orbital CCSD(T) approximations, ultimately finding an affordable localized natural orbital CCSD(T) [LNO-CCSD(T)]-based post-MP2 correction that agrees to 0.006 kcal/mol mean absolute deviation with the revised canonical reference data. In tandem with canonical MP2-F12 complete basis set extrapolation, this was then used to re-evaluate the ACONF16 and ACONF20 subsets for n-hexadecane and n-icosane, respectively. Combining those with the revised canonical reference data for the dodecane conformers (i.e., ACONF12 subset), a revised ACONFL set was obtained. It was then used to assess the performance of different localized-orbital coupled-cluster approaches, such as pair natural orbital localized CCSD(T) [PNO-LCCSD(T)] as implemented in MOLPRO, DLPNO-CCSD(T0) and DLPNO-CCSD(T1) as implemented in ORCA, and LNO-CCSD(T) as implemented in MRCC, at their respective "Normal", "Tight", "vTight", and "vvTight" accuracy settings. For a given accuracy threshold and basis set, DLPNO-CCSD(T1) and DLPNO-CCSD(T0) perform comparably. With "VeryTightPNO" cutoffs, explicitly correlated DLPNO-CCSD(T1)-F12/VDZ-F12 is the best pick among all the DLPNO-based methods tested. To isolate basis set incompleteness from localized-orbital-related truncation errors (domain, LNOs), we have also compared the localized coupled-cluster approaches with canonical DF-CCSD(T)/aug-cc-pVTZ for the ACONF12 set. We found that gradually tightening the cutoffs improves the performance of LNO-CCSD(T), and using a composite scheme such as vTight + 0.50[vTight - Tight] improves things further. For DLPNO-CCSD(T1), "TightPNO" and "VeryTightPNO" offer a statistically similar accuracy, which gets slightly better when TCutPNO is extrapolated to the complete PNO space limit. Similar to Brauer et al.'s [Phys. Chem. Chem. Phys.2016,18 (31), 20905-20925] previous report for the S66x8 noncovalent interactions, the dispersion-corrected direct random phase approximation (dRPA)-based double hybrids perform remarkably well for the ACONFL set. While the revised reference data do not affect any conclusions on the less accurate methods, they may upend orderings for more accurate methods with error statistics on the same order as the difference between reference datasets.

Approaching the basis-set limit of the dRPA correlation energy with explicitly correlated and projector augmented-wave methods

The direct random-phase approximation (dRPA) is used to calculate and compare atomization energies for the HEAT set and ten selected molecules of the G2-1 set using both plane waves and Gaussian-type orbitals. We describe detailed procedures to obtain highly accurate and well converged results for the projector augmented-wave method as implemented in the Vienna Ab initio Simulation Package as well as the explicitly correlated dRPA-F12 method as implemented in the TURBOMOLE package. The two approaches agree within chemical accuracy (1 kcal/mol) for the atomization energies of all considered molecules, both for the exact exchange as well as for the RPA. The root mean-square deviation is 0.41 kcal/mol for the exact exchange (evaluated using density functional theory orbitals) and 0.33 kcal/mol for exact exchange plus correlation from the RPA.

Scaled σ-functionals for the Kohn-Sham correlation energy with scaling functions from the homogeneous electron gas.

The recently introduced σ-functionals constitute a new type of functionals for the Kohn-Sham (KS) correlation energy. σ-Functionals are based on the adiabatic-connection fluctuation-dissipation theorem, are computationally closely related to the well-known direct random phase approximation (dRPA), and are formally rooted in many-body perturbation theory along the adiabatic connection. In σ-functionals, the function of the eigenvalues σ of the Kohn-Sham response matrix that enters the coupling constant and frequency integration in the dRPA is replaced by another function optimized with the help of reference sets of atomization, reaction, transition state, and non-covalent interaction energies. σ-Functionals are highly accurate and yield chemical accuracy of 1 kcal/mol in reaction or transition state energies, in main group chemistry. A shortcoming of σ-functionals is their inability to accurately describe processes involving a change of the electron number, such as ionizations or electron attachments. This problem is attributed to unphysical self-interactions caused by the neglect of the exchange kernel in the dRPA and σ-functionals. Here, we tackle this problem by introducing a frequency- and σ-dependent scaling of the eigenvalues σ of the KS response function that models the effect of the exchange kernel. The scaling factors are determined with the help of the homogeneous electron gas. The resulting scaled σ-functionals retain the accuracy of their unscaled parent functionals but in addition yield very accurate ionization potentials and electron affinities. Moreover, atomization and total energies are found to be exceptionally accurate. Scaled σ-functionals are computationally highly efficient like their unscaled counterparts.

An assessment of orbital energy corrections for the direct random phase approximation and explicit σ-functionals

The σ-functionals developed in the Görling group [J. Chem. Phys. 154, 014104 (2021); ibid. 155, 134111 (2021)] facilitate impressive improvements over the direct random phase approximation (dRPA) and provide chemical accuracy for a broad spectrum of benchmarks concerning reaction energies and barrier heights, but struggle considerably with problems related to self-interaction. We herein assess two possible corrections to the orbital energies in the construction of the non-interacting response function for the dRPA and σ-functionals: (i) The scaling corrections of Yang and co-workers, which have been successfully applied within DFT, and (ii) the admixture of exact exchange in a post-SCF fashion similar to some double-hybrid functionals. An analysis of static shifts to the virtual orbital energies reveals the choice of corrections to be a difficult balancing act, as the effect of the corrections vastly differs between benchmark sets. Scaling corrections are found to provide substantial improvements to self-interaction problems, but seem adversarial for thermochemistry in combination with RPA. The post-SCF inclusion of exact exchange in combination with a semicanonical projection is shown to retain the accuracy of σ-functionals over a wide range of exact exchange admixtures and reduces the computational cost of the SCF calculation compared to hybrid functionals, but provides smaller improvements to self-interaction problems than scaling corrections for the most challenging cases.

Surface science using coupled cluster theory via local Wannier functions and in-RPA-embedding: The case of water on graphitic carbon nitride.

A first-principles study of the adsorption of a single water molecule on a layer of graphitic carbon nitride is reported employing an embedding approach for many-electron correlation methods. To this end, a plane-wave based implementation to obtain intrinsic atomic orbitals and Wannier functions for arbitrary localization potentials is presented. In our embedding scheme, the localized occupied orbitals allow for a separate treatment of short-range and long-range correlation contributions to the adsorption energy by a fragmentation of the simulation cell. In combination with unoccupied natural orbitals, the coupled cluster ansatz with single, double, and perturbative triple particle-hole excitation operators is used to capture the correlation in local fragments centered around the adsorption process. For the long-range correlation, a seamless embedding into the random phase approximation yields rapidly convergent adsorption energies with respect to the local fragment size. Convergence of computed binding energies with respect to the virtual orbital basis set is achieved employing a number of recently developed techniques. Moreover, we discuss fragment size convergence for a range of approximate many-electron perturbation theories. The obtained benchmark results are compared to a number of density functional calculations.

Benchmarking the Accuracy of the Direct Random Phase Approximation and σ-Functionals for NMR Shieldings.

A method for computing NMR shieldings with the direct random phase approximation (RPA) and the closely related σ-functionals [Trushin, E.; Thierbach, A.; Görling, A. Toward chemical accuracy at low computational cost: density functional theory with σ-functionals for the correlation energy. J. Chem. Phys. 2021, 154, 014104] is presented, which is based on a finite-difference approach. The accuracy is evaluated in benchmark calculations using high-quality coupled cluster values as a reference. Our results show that the accuracy of the computed NMR shieldings using direct RPA is strongly dependent on the density functional theory reference orbitals and improves with increasing amounts of exact Hartree-Fock exchange in the functional. NMR shieldings computed with direct RPA using a Hartree-Fock reference are significantly more accurate than MP2 shieldings and comparable to CCSD shieldings. Also, the basis set convergence is analyzed and it is shown that at least triple-zeta basis sets are required for reliable results.

Towards efficient description of type-C London dispersion forces between low-dimensional metallic nanostructures

This paper concerns one of the remaining difficulties encountered in efficient modelling schemes for dispersion forces between nanostructures. Dispersion (van der Waals, vdW) interactions between molecules and nanostructures can be reliably described in principle by computationally intensive high-level theory, but this is often not computationally feasible in practice, so more efficient methods are continually being developed. Progress has been made with nonlocal density functionals (vdW-DFs) and with atom-based schemes (D4, MBD, uMBD). In such efficient schemes, the effects beyond additive two-atom terms have been categorized as ‘type A’, ‘type B’ and ‘type C’ non-additivity (see Dobson (2014 Int. J. Quantum Chem. 114 1157)). Atom-based models using coupled-harmonic-oscillator theory (MBD) now deal adequately with type A and type B non-additivity, but type-C effects, related to gapless collective electronic excitations, can occur in low-dimensional metals, and these are not correctly described by the efficient schemes mentioned above.From analytic work within the direct random phase approximation (dRPA), type-C effects have long been known to cause the vdW interaction between well-separated low-d metals to fall off much more slowly with separation than is predicted by the above-mentioned efficient schemes. The slower decay means that type-C effects dominate in this asymptotic large-separation regime. It has not been clear, however, whether type-C physics contributes significantly to the vdW interaction of low-d metals near to contact, where the forces are much larger.The present work uses recent semi-analytic dRPA results to provide some evidence that type-C effects are indeed significant near to contact between metallic carbon nanotubes, and between doped graphene sheets.Some guidelines are therefore suggested for ways to combine the semi-analytic dRPA approach, here termed ‘SAM-dRPA’, with the existing efficient vdW algorithms described above.

Chemical accuracy with σ-functionals for the Kohn-Sham correlation energy optimized for different input orbitals and eigenvalues.

Recently, a new type of orbital-dependent functional for the Kohn-Sham (KS) correlation energy, σ-functionals, was introduced. Technically, σ-functionals are closely related to the well-known direct random phase approximation (dRPA). Within the dRPA, a function of the eigenvalues σ of the frequency-dependent KS response function is integrated over purely imaginary frequencies. In σ-functionals, this function is replaced by one that is optimized with respect to reference sets of atomization, reaction, transition state, and non-covalent interaction energies. The previously introduced σ-functional uses input orbitals and eigenvalues from KS calculations with the generalized gradient approximation (GGA) exchange-correlation functional of Perdew, Burke, and Ernzerhof (PBE). Here, σ-functionals using input orbitals and eigenvalues from the meta-GGA TPSS and the hybrid-functionals PBE0 and B3LYP are presented and tested. The number of reference sets taken into account in the optimization of the σ-functionals is larger than in the first PBE based σ-functional and includes sets with 3d-transition metal compounds. Therefore, also a reparameterized PBE based σ-functional is introduced. The σ-functionals based on PBE0 and B3LYP orbitals and eigenvalues reach chemical accuracy for main group chemistry. For the 10966 reactions from the highly accurate W4-11RE reference set, the B3LYP based σ-functional exhibits a mean average deviation of 1.03 kcal/molcompared to 1.08 kcal/molfor the coupled cluster singles doubles perturbative triples method if the same valence quadruple zeta basis set is used. For 3d-transition metal chemistry, accuracies of about 2 kcal/molare reached. The computational effort for the post-self-consistent evaluation of the σ-functional is lower than that of a preceding PBE0 or B3LYP calculation for typical systems.

Energies, structures, and harmonic frequencies of small water clusters from the direct random phase approximation.

The binding energies, structures, and vibrational frequencies of water clusters up to 20 molecules are computed at the direct random phase approximation (RPA) level of theory and compared to theoretical benchmarks. Binding energies of the WATER27 set, which includes neutral and positively and negatively charged clusters, are predicted to be too low in the complete basis set limit by an average of 7 kcal/mol (9%) and are worse than the results from the best density functional theory methods or from the Møller-Plesset theory. The RPA shows significant basis set size dependence for binding energies. The order of the relative energies of the water hexamer and dodecamer isomers is predicted correctly by the RPA. The mean absolute deviation for angles and distances for neutral clusters up to the water hexamer are 0.2° and 0.6pm, respectively, using quintuple-ζ basis sets. The relative energetic order of the hexamer isomers is preserved upon optimization. Vibrational frequencies for these systems are underestimated by several tens of wavenumbers for large basis sets, and deviations increase with the basis set size. Overall, the direct RPA method yields accurate structural parameters but systematically underestimates binding energies and shows strong basis set size dependence.

Numerically stable optimized effective potential method with standard Gaussian basis sets.

We present a numerically stable optimized effective potential (OEP) method based on Gaussian basis sets. The key point of the approach is a sequence of preprocessing steps of the auxiliary basis set used to represent exchange or correlation potentials, the Kohn-Sham (KS) response function, and the right-hand side of the OEP equation in conjunction with a representation of exchange or correlation potentials via exchange or correlation charge densities whose electrostatic potentials generate the potentials. Due to the preprocessing, standard Gaussian basis sets from basis set libraries can be used in OEP calculations. As examples, we present numerical stable computational setups based on aux-cc-pwCVXZ basis sets with X = T, Q, 5 for the orbitals and aux-cc-pVDZ/mp2fit and aux-cc-pVTZ/mp2fit auxiliary basis sets and use them to calculate KS exchange potentials with the exact exchange-only KS method for various atoms and molecules. The resulting exchange potentials not only are numerically stable and physically reasonable but also show convergence with increasing quality of the orbital basis sets. The effect of incorporating exact conditions that the KS exchange potential has to obey is discussed. Moreover, it is briefly demonstrated that the presented approach not only works for KS exchange potentials but equally well for correlation potentials within the direct random phase approximation. Besides for OEP methods, the introduced preprocessing of auxiliary basis sets should also be beneficial in procedures to calculate back effective KS potentials from given electron densities.

Cerium Oxides without U: The Role of Many-Electron Correlation.

Electron transfer with changing occupation in the 4f subshell poses a considerable challenge for quantitative predictions in quantum chemistry. Using the example of cerium oxide, we identify the main deficiencies of common parameter-dependent one-electron approaches, such as density functional theory (DFT) with a Hubbard correction, or hybrid functionals. As a response, we present the first benchmark of ab initio many-electron theory for electron transfer energies and lattice parameters under periodic boundary conditions. We show that the direct random phase approximation clearly outperforms all DFT variations. From this foundation, we, then, systematically improve even further. Periodic second-order Møller–Plesset perturbation theory meanwhile manages to recover standard hybrid functional values. Using these approaches to eliminate parameter bias allows for highly accurate benchmarks of strongly correlated materials, the reliable assessment of various density functionals, and functional fitting via machine-learning.

Exploring Avenues beyond Revised DSD Functionals: II. Random-Phase Approximation and Scaled MP3 Corrections.

For revDSD double hybrids, the Görling–Levy second-order perturbation theory component is an Achilles’ heel when applied to systems with significant near-degeneracy (“static”) correlation. We have explored its replacement by the direct random phase approximation (dRPA), inspired by the SCS-dRPA75 functional of Kállay and co-workers. The addition to the final energy of both a D4 empirical dispersion correction and of a semilocal correlation component lead to significant improvements, with DSD-PBEdRPA75-D4 approaching the performance of revDSD-PBEP86-D4 and the Berkeley ωB97M(2). This form appears to be fairly insensitive to the choice of the semilocal functional but does exhibit stronger basis set sensitivity than the PT2-based double hybrids (due to much larger prefactors for the nonlocal correlation). As an alternative, we explored adding an MP3-like correction term (in a medium-sized basis set) to a range-separated ωDSD-PBEP86-D4 double hybrid and found it to have significantly lower WTMAD2 (weighted mean absolute deviation) for the large and chemically diverse GMTKN55 benchmark suite; the added computational cost can be mitigated through density fitting techniques.

Local embedding of coupled cluster theory into the random phase approximation using plane waves.

We present an embedding approach to treat local electron correlation effects in periodic environments. In a single consistent framework, our plane wave based scheme embeds a local high-level correlation calculation [here, Coupled Cluster (CC) theory], employing localized orbitals, into a low-level correlation calculation [here, the direct Random Phase Approximation (RPA)]. This choice allows for an accurate and efficient treatment of long-range dispersion effects. Accelerated convergence with respect to the local fragment size can be observed if the low-level and high-level long-range dispersions are quantitatively similar, as is the case for CC in RPA. To demonstrate the capabilities of the introduced embedding approach, we calculate adsorption energies of molecules on a surface and in a chabazite crystal cage, as well as the formation energy of a lattice impurity in a solid at the level of highly accurate many-electron perturbation theories. The absorption energy of a methane molecule in a zeolite chabazite is converged with an error well below 20 meV at the CC level. As our largest periodic benchmark system, we apply our scheme to the adsorption of a water molecule on titania in a supercell containing more than 1000 electrons.

Toward chemical accuracy at low computational cost: Density-functional theory with σ-functionals for the correlation energy.

We introduce new functionals for the Kohn-Sham correlation energy that are based on the adiabatic-connection fluctuation-dissipation (ACFD) theorem and are named σ-functionals. Like in the well-established direct random phase approximation (dRPA), σ-functionals require as input exclusively eigenvalues σ of the frequency-dependent KS response function. In the new functionals, functions of σ replace the σ-dependent dRPA expression in the coupling-constant and frequency integrations contained in the ACFD theorem. We optimize σ-functionals with the help of reference sets for atomization, reaction, transition state, and non-covalent interaction energies. The optimized functionals are to be used in a post-self-consistent way using orbitals and eigenvalues from conventional Kohn-Sham calculations employing the exchange-correlation functional of Perdew, Burke, and Ernzerhof. The accuracy of the presented approach is much higher than that of dRPA methods and is comparable to that of high-level wave function methods. Reaction and transition state energies from σ-functionals exhibit accuracies close to 1 kcal/mol and thus approach chemical accuracy. For the 10 966 reactions of the W4-11RE reference set, the mean absolute deviation is 1.25 kcal/mol compared to 3.21 kcal/mol in the dRPA case. Non-covalent binding energies are accurate to a few tenths of a kcal/mol. The presented approach is highly efficient, and the post-self-consistent calculation of the total energy requires less computational time than a density-functional calculation with a hybrid functional and thus can be easily carried out routinely. σ-Functionals can be implemented in any existing dRPA code with negligible programming effort.

Analytic energy gradients for the self-consistent direct random phase approximation.

Analytic energy gradients with respect to nuclear coordinates are derived and implemented for the self-consistent direct random phase approximation (sc-dRPA) method. In contrast to the more common non-self-consistent dRPA methods, the sc-dRPA method does not require a choice for the approach to generate the Kohn-Sham orbitals and eigenvalues serving as input for the dRPA correlation functional. The fact that the sc-dRPA total energy is variational facilitates the calculation of analytic gradients. The analytic gradients are tested against numerical ones and then used to calculate equilibrium geometries and vibrational frequencies for various molecules including weakly bonded dimers and transition metal compounds. The sc-dRPA method can compete in accuracy with Møller-Plesset perturbation theory of second order and with conventional density-functional methods within the generalized gradient approximation or of hybrid type. Indeed, sc-dRPA geometries and vibrational frequencies are most accurate in many cases. Moreover, the sc-dRPA method is robust in the sense that it is applicable to all considered molecules, whereas conventional density-functional methods are not applicable to dispersion bonded dimers, and Møller-Plesset perturbation theory of second order erroneously predicts a number of molecules to be unbound and yields completely wrong vibrational frequencies in some cases. The coupled cluster singles doubles methods yield geometries and vibrational frequencies of a quality that is inferior to that of the other considered methods.