corrections Sec. I
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@ -113,13 +113,13 @@ Loosely speaking, to make any method practical, three main approximations must b
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The first fundamental approximation, known as the Born-Oppenheimer (or clamped-nuclei) approximation, consists in assuming that the motion of nuclei and electrons are decoupled. \cite{Born_1927}
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The first fundamental approximation, known as the Born-Oppenheimer (or clamped-nuclei) approximation, consists in assuming that the motion of nuclei and electrons are decoupled. \cite{Born_1927}
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The nuclei coordinates can then be treated as parameters in the electronic Hamiltonian.
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The nuclei coordinates can then be treated as parameters in the electronic Hamiltonian.
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The second central approximation which makes calculations feasible by a computer is the basis set approximation where one introduces a set of pre-defined basis functions to represent the many-electron wave function of the system.
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The second central approximation which makes calculations feasible by a computer is the basis set approximation where one introduces a set of pre-defined basis functions to represent the many-electron wave function of the system.
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In most molecular calculations, a set of one-electron, atom-centered gaussian basis functions are introduced to expand the so-called one-electron molecular orbitals which are then used to build the many-electron Slater determinants.
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In most molecular calculations, a set of one-electron, atom-centered Gaussian basis functions are introduced to expand the so-called one-electron molecular orbitals which are then used to build the many-electron Slater determinants.
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The third and most relevant approximation in the present context is the ansatz (or form) of the electronic wave function $\Psi$.
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The third and most relevant approximation in the present context is the ansatz (or form) of the electronic wave function $\Psi$.
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For example, in configuration interaction (CI) methods, the wave function is expanded as a linear combination of Slater determinants, while in (single-reference) coupled-cluster (CC) theory, \cite{Cizek_1966,Paldus_1972,Crawford_2000,Piecuch_2002b,Bartlett_2007,Shavitt_2009} a reference Slater determinant $\PsiO$ [usually taken as the Hartree-Fock (HF) wave function] is multiplied by a wave operator defined as the exponentiated excitation operator $\hT = \sum_{k=1}^\Nel \hT_k$ (where $\Nel$ is the number of electrons).
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For example, in configuration interaction (CI) methods, the wave function is expanded as a linear combination of Slater determinants, while in (single-reference) coupled-cluster (CC) theory, \cite{Cizek_1966,Paldus_1972,Crawford_2000,Piecuch_2002b,Bartlett_2007,Shavitt_2009} a reference Slater determinant $\PsiO$ [usually taken as the Hartree-Fock (HF) wave function] is multiplied by a wave operator defined as the exponentiated excitation operator $\hT = \sum_{k=1}^\Nel \hT_k$ (where $\Nel$ is the number of electrons).
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The truncation of $\hT$ allows to define a hierarchy of non-variational and size-extensive methods with improved accuracy:
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The truncation of $\hT$ allows to define a hierarchy of non-variational and size-extensive methods with increasing levels of accuracy:
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CC with singles and doubles (CCSD), \cite{Cizek_1966,Purvis_1982} CC with singles, doubles, and triples (CCSDT), \cite{Noga_1987a,Scuseria_1988} CC with singles, doubles, triples, and quadruples (CCSDTQ), \cite{Oliphant_1991,Kucharski_1992} with corresponding computational scalings of $\order*{\Norb^{6}}$, $\order*{\Norb^{8}}$, and $\order*{\Norb^{10}}$, respectively (where $\Norb$ denotes the number of orbitals).
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CC with singles and doubles (CCSD), \cite{Cizek_1966,Purvis_1982} CC with singles, doubles, and triples (CCSDT), \cite{Noga_1987a,Scuseria_1988} CC with singles, doubles, triples, and quadruples (CCSDTQ), \cite{Oliphant_1991,Kucharski_1992} with corresponding computational scalings of $\order*{\Norb^{6}}$, $\order*{\Norb^{8}}$, and $\order*{\Norb^{10}}$, respectively (where $\Norb$ denotes the number of orbitals).
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Parallel to the ``complete'' CC series presented above, an alternative family of approximate iterative CC models have been developed by the Aarhus group in the context of CC response theory \cite{Christiansen_1998} where one skips the most expensive terms and avoids the storage of the higher-excitation amplitudes: CC2, \cite{Christiansen_1995a} CC3, \cite{Christiansen_1995b,Koch_1997} and CC4. \cite{Kallay_2005,Matthews_2021}
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Parallel to the ``complete'' CC series presented above, an alternative family of approximate iterative CC models has been developed by the Aarhus group in the context of CC response theory \cite{Christiansen_1998} where one skips the most expensive terms and avoids the storage of the higher-excitation amplitudes: CC2, \cite{Christiansen_1995a} CC3, \cite{Christiansen_1995b,Koch_1997} and CC4. \cite{Kallay_2005,Matthews_2021}
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These iterative methods scale as $\order*{\Norb^{5}}$, $\order*{\Norb^{7}}$, and $\order*{\Norb^{9}}$, respectively, and can be seen as cheaper approximations of CCSD, CCSDT, and CCSDTQ.
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These iterative methods scale as $\order*{\Norb^{5}}$, $\order*{\Norb^{7}}$, and $\order*{\Norb^{9}}$, respectively, and can be seen as cheaper approximations of CCSD, CCSDT, and CCSDTQ.
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Coupled-cluster methods have been particularly successful at computing accurately various properties for small- and medium-sized molecules.
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Coupled-cluster methods have been particularly successful at computing accurately various properties for small- and medium-sized molecules.
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\cite{Kallay_2003,Kallay_2004a,Gauss_2006,Kallay_2006,Gauss_2009,Chrayteh_2021,Sarkar_2021}
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\cite{Kallay_2003,Kallay_2004a,Gauss_2006,Kallay_2006,Gauss_2009,Chrayteh_2021,Sarkar_2021}
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@ -136,7 +136,7 @@ Although the formal scaling of such algorithms remains exponential, the prefacto
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Note that, very recently, several groups \cite{Aroeira_2021,Lee_2021,Magoulas_2021} have coupled CC and SCI methods via the externally-corrected CC methodology, \cite{Paldus_2017} showing promising performances for weakly and strongly correlated systems.
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Note that, very recently, several groups \cite{Aroeira_2021,Lee_2021,Magoulas_2021} have coupled CC and SCI methods via the externally-corrected CC methodology, \cite{Paldus_2017} showing promising performances for weakly and strongly correlated systems.
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A rather different strategy in order to reach the holy grail FCI limit is to resort to M{\o}ller-Plesset (MP) perturbation theory, \cite{Moller_1934}
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A rather different strategy in order to reach the holy grail FCI limit is to resort to M{\o}ller-Plesset (MP) perturbation theory, \cite{Moller_1934}
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which popularity originates from its black-box nature, size-extensivity, and relatively low computational scaling, making it easily applied to a broad range of molecular systems.
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whose popularity originates from its black-box nature, size-extensivity, and relatively low computational scaling, making it easily applied to a broad range of molecular systems.
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Again, at least in theory, one can obtain the exact energy of the system by ramping up the degree of the perturbative series. \cite{Marie_2021}
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Again, at least in theory, one can obtain the exact energy of the system by ramping up the degree of the perturbative series. \cite{Marie_2021}
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The second-order M{\o}ller-Plesset (MP2) method \cite{Moller_1934} [which scales as $\order*{\Norb^{5}}$] has been broadly adopted in quantum chemistry for several decades, and is now included in the increasingly popular double-hybrid functionals \cite{Grimme_2006} alongside exact HF exchange.
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The second-order M{\o}ller-Plesset (MP2) method \cite{Moller_1934} [which scales as $\order*{\Norb^{5}}$] has been broadly adopted in quantum chemistry for several decades, and is now included in the increasingly popular double-hybrid functionals \cite{Grimme_2006} alongside exact HF exchange.
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Its higher-order variants [MP3, \cite{Pople_1976}
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Its higher-order variants [MP3, \cite{Pople_1976}
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