Implicit Solvation Models#
隐式溶剂模型

One aproach to include solvent effects on your calculation is through the so-called "implicit solvent models", and here we will discuss two main options available in ORCA.
一种将溶剂效应纳入计算的方法是通过所谓的“隐式溶剂模型”，在此我们将讨论 ORCA 中可用的两种主要选项。

Overview# 概述

In these models, the solute is placed in a cavity of roughly molecular shape. The solvent is described by a continuum that interacts with the charges on the cavity surface, which are in turn determined by the solute and the problem is solved iteratively (see [Cammi2005] for a good review on the subject).
在这些模型中，溶质被置于一个大致呈分子形状的空腔内。溶剂则通过一个连续体来描述，该连续体与空腔表面的电荷相互作用，而这些电荷又由溶质决定，问题通过迭代求解（参见[Cammi2005]以获得对该主题的详尽综述）。

The general picture of the method can be depicted as:
该方法的总体图景可以描述为：

where the "probe" is an ideal solvent molecule and the molecular cavities are defined from:
其中，“探针”为理想溶剂分子，分子腔由以下定义：

"Van der Waals surface" (vdW), built from the Van der Waals radii (the default in ORCA);
范德华表面（vdW），基于范德华半径构建（ORCA 中的默认设置）；

"Solvent-Accessible Surface" (SAS), defined by the center of the probe;
溶剂可及表面（SAS），由探针中心定义；

or the "Solvent-Excluded Surface" (SES), obtained if you follow the inward part of the solvent probe sphere rolling over vdW surface.
或称为“溶剂排除表面”（SES），即当溶剂探针球沿范德华表面内侧滚动时所获得的表面。

An exemplary visualization of the SES for a cyclodextrine molecule is shown below:
以下展示了一个环糊精分子空间填充模型的典型可视化示例：

../_images/cyclodex-ses-transparency40.png — Figure: SES for a cyclodextrine molecule.
图：环糊精分子的 SES。#

The solvation energy is then decomposed in two main terms, electrostatic ( $Δ G_{E N P}$ ) and cavity-dispersion ( $Δ G_{C D S}$ ):
溶剂化能随后被分解为两个主要项：静电项（ $Δ G_{E N P}$ ）和空腔-色散项（ $Δ G_{C D S}$ ）：

Δ G_{s o l v}^{o} = Δ G_{E N P} + Δ G_{C D S}

and the methods differ on how to compute these terms.
计算这些项的方法有所不同。

Transition from Gas to Liquid phase#
气相到液相的转变

Depending on the desired reference state of your molecule, an additional term to the solvation free energy has to be included:
根据所需分子参考态的不同，溶剂化自由能中需包含一个附加项：

Δ G_{s o l v}^{o} = Δ G_{E N P} + Δ G_{C D S} + Δ G_{c o n c}^{o}

This term arises when going from gas phase at $1 a t m$ and $298 K$ (which is how the $G^{o}$ is calculated when using FREQ by default) to a solution phase at $1 m o l L^{- 1}$ . The corresponding correction [Cramer2004] is:
当从 $1 a t m$ 和 $298 K$ 的气相（这是在使用 FREQ 时默认计算 $G^{o}$ 的方式）转变到 $1 m o l L^{- 1}$ 的溶液相时，会出现这一术语。相应的修正[Cramer2004]为：

Δ G_{c o n c}^{o} = R T l n (24.5) = 1.89 k c a l / m o l .

Warning 警告

Do not forget to add this term to your $G^{o}$ when predicting solution thermodynamics. The absence of this correction can lead to large errors!
在预测溶液热力学时，别忘了将此项加入你的 $G^{o}$ 中。缺少此修正可能导致巨大误差！

Conductor-like Polarizable Continuum Model (CPCM)#
导体类极化连续介质模型 (CPCM)

In the CPCM method [Cossi1998], the bulk solvent is treated as a conductor-like polarizable continuum and the main parameters to define the method are the refractive index and the dielectric constant of the medium.
在 CPCM 方法[Cossi1998]中，溶剂整体被视为类导体可极化连续体，定义该方法的主要参数是介质的折射率和介电常数。

The electrostatic contribution ( $Δ G_{E N P}$ ) that arises from the interaction of the medium and the molecular surface charges is included in the SCF calculation - so that you even get "solvated" orbitals - and the cavity term ( $Δ G_{C D S}$ ) can be obtained from more complicated schemes.
介质与分子表面电荷相互作用产生的静电贡献（ $Δ G_{E N P}$ ）被纳入 SCF 计算中——因此您甚至可以获得“溶剂化”轨道——而空腔项（ $Δ G_{C D S}$ ）则可通过更复杂的方案求得。

ORCA has a list of predefined solvents that can be called by using:
ORCA 提供了一系列预定义溶剂，可通过以下方式调用：

!CPCM(solvent)

A full list of available solvents is given in the end of this tutorial.
本教程末尾提供了可用溶剂的完整列表。

If you want to include any other solvent, one can always input these parameters manually using:
如果你想包含其他溶剂，可以随时手动输入这些参数：

%CPCM       EPSILON      80.4
            REFRAC       1.33
END

More options and details can be found on the ORCA manual. One example for the single-point calculation of an Aspirin molecule in water is:
更多选项和详细信息可在 ORCA 手册中找到。例如，阿司匹林分子在水中的单点计算示例如下：

!B97M-V DEF2-SVP CPCM(WATER)
* XYZFILE 0 1 aspirin.xyz

Note 注释

Both the analytic gradients and Hessians are available for the CPCM, so that can be used together with the OPT and FREQ keywords as well!
CPCM 的解析梯度和 Hessian 矩阵均可获得，因此可以与 OPT 和 FREQ 关键字一同使用！

Then, before the SCF, a header with all the CPCM-related information is printed:
然后，在自洽场计算之前，会打印一个包含所有 CPCM 相关信息的头部：

--------------------                               
CPCM SOLVATION MODEL
--------------------
CPCM parameters:
  Epsilon                                         ...      80.1510
  Refrac                                          ...       1.3328
  Rsolv                                           ...       1.3000
  Surface type                                    ... GAUSSIAN VDW
  Discretization scheme                           ... Constant charge density
    Threshold for H atoms                         ...       5.0000 (charges/Ang^2)
    Threshold for non-H atoms                     ...       5.0000 (charges/Ang^2)
  Epsilon function type                           ...         CPCM
Solvent:                                          ... WATER
Radii:
  Scheme                                          ... Element-dependent radii
  Radius for C  used is    3.8550 Bohr (=   2.0400 Ang.)
  Radius for O  used is    3.4469 Bohr (=   1.8240 Ang.)
  Radius for H  used is    2.4944 Bohr (=   1.3200 Ang.)
Calculating surface                               ...        done! (  0.0s)
Cavity surface points                             ...         2001
Cavity Volume                                     ...    1411.7200
Cavity Surface-area                               ...     764.1268
Calculating surface distance matrix               ...        done! (  0.0s)
Performing Cholesky decomposition & store         ...        done! (  0.1s)
Overall time for CPCM initialization              ...                 0.1s

after the SCF calculation ends, there will be a the summary of the CPCM-related information:
SCF 计算结束后，将显示 CPCM 相关信息的摘要：

----------------
TOTAL SCF ENERGY
----------------

Total Energy       :       -648.14295834055463 Eh          -17636.86654 eV

Components:
Nuclear Repulsion  :        765.01084602209096 Eh           20817.00344 eV
Electronic Energy  :      -1413.49491093482038 Eh          -38463.15196 eV
One Electron Energy:      -2400.15868861270292 Eh          -65311.63830 eV
Two Electron Energy:        986.66377767788265 Eh           26848.48634 eV
CPCM Dielectric    :         -0.02002640002963 Eh              -0.54495 eV
[...]
CPCM Solvation Model Properties:
Surface-charge          :         -0.01495190657874
Corrected charge        :          0.00000000000000
Outlying charge corr.   :          0.00001461700770 Eh               0.00040 eV
Free-energy (cav+disp)  :  This term is not implemented in the current solvation scheme

As one can see, dielectric contribution to the energy, the solute net charge, the charge and cavity corrections are printed separately (the latter in this case is not calculated). The Charge-correction term is not included in the SCF energy, and is just printed for information purposes.
如所见，介电能量贡献、溶质净电荷、电荷及空腔修正分别列出（后者在此情况下未计算）。 Charge-correction 项不纳入 SCF 能量计算，仅作信息打印。

The FINAL SINGLE POINT ENERGY now already includes all computed solvation terms. In terms of the equations shown above, $Δ G_{E N P}$ corresponds to CPCM Dielectric and $Δ G_{C D S}$ to the Free-energy (cav+disp).
最终单点能现已包含所有计算的溶剂化项。根据上述方程， $Δ G_{E N P}$ 对应于 CPCM Dielectric ，而 $Δ G_{C D S}$ 对应于 Free-energy (cav+disp) 。

Important 重要

There is an important difference with respect to previous ORCA versions. Now the cavity term is not calculated or added for regular CPCM by default.
与之前的 ORCA 版本相比，存在一个重要差异。现在，默认情况下，常规 CPCM 的空腔项不再计算或添加。

Note 注释

For more information on cavity terms and CPCM, please consult the ORCA manual.
有关腔体术语和 CPCM 的更多信息，请参阅 ORCA 手册。

CPCM and COSMO#

ORCA does not have any COSMO implementation, but one can use the COSMO epsilon function by using the CPCMC(solvent) keyword, with an extra "C":

!B97M-V DEF2-SVP CPCMC(WATER)

Combining DFT with post-HF methods#

Since the HF density is of lower quality than those obtained from DFT, so is the CPCM correction obtained from HF calculations.

What one usually can do is to take the $Δ G_{E N P}$ (CPCM Dielectric) and $Δ G_{C D S}$ (Free-energy (cav+disp)) from some calculation like DFT and add that to the total energy obtained with that method, e.g. if you want to combine CPCM with DLPNO-CSSD.

Gaussian point charges#

The usual point charge scheme might lead to instabilities in the energy, e.g. if two points end up too close. In ORCA, we use a smeared Gaussian charge to obtain a smoother potential energy surface [Karplus1999] [Neese2020] instead. From ORCA 5, the default is:

%CPCM SURFACETYPE VDW_GAUSSIAN END

But a SES surface can also be chosen with:

%CPCM SURFACETYPE GEPOL_SES_GAUSSIAN END

For more detailed information, please consult the ORCA manual.

Universal Solvation Model (SMD)#

The SMD method [Truhlar2009] can be thought as an improvement over the CPCM, since it uses the full solute electron density to compute the cavity-dispersion contribution instead of the area only.

This method requires more parameters, which makes it less flexible for unknown solvents (List of available solvents)! SMD can be requested similar to CPCM via simple input SMD(Solvent):

!B97M-V DEF2-SVP SMD(WATER)

* XYZFILE 0 1 aspirin.xyz

The initial output is similar to CPCM, except that one now has the SMD descriptors:

--------------------
CPCM SOLVATION MODEL
--------------------
[...]
SMD-CDS solvent descriptors:
  Soln                                       ...    1.3328
  Soln25                                     ...    1.3323
  Sola                                       ...    0.0000
  Solb                                       ...    0.0000
  Solg                                       ...    0.0000
  Solc                                       ...    0.0000
  Solh                                       ...    0.0000

and the output before the the TOTAL SCF ENERGY header has:

----------------
TOTAL SCF ENERGY
----------------                                  
[...]
CPCM Dielectric    :         -0.03176518706751 Eh              -0.86437 eV
SMD CDS (Gcds)     :          0.01088483110166 Eh               0.29619 eV

One can use this $Δ G_{C D S}$ (Gcds) term, together with the $Δ G_{E N P}$ (CPCM Dielectric) to correct energies from further calculations.

Note

With ORCA 6, analytic gradients became available also for SMD!

Dynamic Radii Adjustment for Continuum Solvation (DRACO)#

All these solvation models depend on a physically sound representation of the solvent accessible surface area (SASA). Nevertheless, the typically employed methods use a predefined set of element specific atomic radii to construct it. This does not account for the molecular environment of specific atoms for which the effective radii may differ depending on the respective local electron density, e.g., if one compares neutral and negatively charged oxygen atoms. A recent approach to make these radii environment adaptive is the DRACO model by Grimme and co-workers [Grimme2024]. It uses an atoms-in-molecules-like approach based on atomic partial charges and fractional coordination numbers to scale the default radii for each atom independently. By doing so, specifically the description of charged systems can be improved.

DRACO is currently available for CPCM and SMD within ORCA and is parameterized for the solvents water, acetonitrile, DMSO, and methanol. DRACO can be envoked by a simple input keyword in addition to the respective solvation method:

! CPCM(solvent) DRACO

! SMD(solvent) DRACO

Alternatively, it can also be requested in the %cpcm block:

%cpcm
DRACO true
end

In ORCA, the default scheme to calculate the partial charges used within DRACO is the electronegativity-equilibration (EEQ) charge model as it is also used in the D4 dispersion correction. However, one can also request the recent Charge Extended Hückel (CEH) model.[Grimme2023] The charge scheme within DRACO is controlled by the following tag in the %cpcm block:

%cpcm
draco_charges ceh  # default = eeq
end

If CEH charges are requested, ORCA generates them via its interface to the xtb program.

Note

At this point, DRACO can only be used in single-point energy calculations. Gradients for DRACO will be implemented in the future.

Example 1: Octanol/water partition coefficient#

We will use SMD and try to predict the octanol/water partition coefficient ( $P_{o / w}$ ) for the drug Diazepam:

P_{o / w} = \frac{[s o l u t e]_{o c t a n o l}}{[s o l u t e]_{w a t e r}}

That can be obtained from the relationship between the equilibrium constant and the Gibb's free energy difference between the solute in octanol and water $Δ G_{o / w}^{o} = Δ G_{o}^{o} - Δ G_{w}^{o}$ as [Truhlar2009]:

l o g P_{o / w} = \frac{- Δ G_{o / w}^{o}}{2.303 R T}

First, we optimize both geometries in each solvent, for instance using:

!B3LYP DEF2-SVP OPT NUMFREQ D4
%CPCM SMD TRUE
      SMDSOLVENT "1-OCTANOL"
END
* XYZFILE 0 1 diazepam.xyz

or:

!B3LYP DEF2-SVP OPT NUMFREQ D4
%CPCM SMD TRUE
      SMDSOLVENT "WATER"
END
* XYZFILE 0 1 diazepam.xyz

to get the Gibbs free energy of each solvated compound and its geometry.

After making the calculations, one obtains an energy difference of $3.41 k c a l / m o l$ , that corresponds to a $l o g P_{o / w} = 2.50$ , which is not far from the experimental value of $l o g P_{o / w}^{e x p} = 2.99$ , considering the simplicity of the method.

Note

Since there are no analytic frequencies using the SMD model yet, we are using !NUMFREQ. It might take long if you do not parallelization here.

Structures Example 1#

openCOSMO-RS#

ORCA is interfaced to openCOSMO-RS,[Gerlach2022] an open source implementation of the COSMO-RS model.[Klamt1995] This model is widely used in both academia and industry to predict fluid phase thermodynamics.

The openCOSMO-RS calculation requires several single-point energy (SPE) evaluations within ORCA:

SPE calculation of the solute in the gas-phase
SPE calculation of the solute in a conductor ( $ϵ = \infty$ )
SPE calculation of the solvent in a conductor ( $ϵ = \infty$ )
Do COSMO-RS via the openCOSMO-RS executable and compute solvation properties

Points 1 to 3 employ the BP86/def2-TZVPD level that was also used to parameterize COSMO-RS for ORCA 6.0.

Warning

Any changes to the DFT level are possible but is strongly discouraged. For details on available settings see the ORCA manual.

COSMO-RS calculations in ORCA are controlled either via simple keyword COSMORS(Solvent) or through the %cosmors block. When called via simple keyword, the solvent structure is read from a database included in ORCA. This is generally recommended. However, individual solvents can be defined via the %cosmors block. In this case, a respective structure file Solvent.cosmorsxyz must be provided. Otherwise, only the solute structure is required. Corresponding inputs look like:

!COSMORS(Solvent)

for using the simple keyword and the solvent from the database. And like:

%cosmors
solvent "Solvent"
end

when the solvent is defined individually.

Example 2: Cyclohexane to water transfer of acetamide#

As an example, we will calculate the free-energy change of the transfer of acetamide from cyclohexane into water.

Even though electronic energies and thermostatistical contributions will cancel out in the end for this specific example, we will perform all calculations that would be needed to obtain a full free-energy in solution for acetamide in both solvents. In general, the full free energy of any compound in solution is calculated as the sum of electronic energy ( $E_{e l .}$ ) in gas-phase, the thermostatistical free-energy correction ( $G_{R R H O}$ ) that is typically obtained from a rigid-rotor-harmonic-oscillator (RRHO) approximation, and the solvation free-energy that can be calculated with openCOSMO-RS ( $δ G_{s o l v .}$ )

G_{s o l v .} = E_{e l .} + G_{R R H O} + δ G_{s o l v .}

Note

Note that for DFT calculations, a London dispersion correction should be added to the electronic energy!

To obtain the corresponding contributions, we will first optimize the geometry of acetamide in the gas-phase and will perform a vibrational frequency calculation to compute thermostatistical contributions:

!r2SCAN-3c TIGHTOPT FREQ

*XYZFILE 0 1 acetamide_unpotimized.xyz

The optimized geometry is stored in basename.xyz and the frequency calculation as well as the thermostatistical corrections can be found in the basename.out output file:

-------------------
GIBBS FREE ENERGY
-------------------

The Gibbs free energy is G = H - T*S
  
Total enthalpy                    ...   -209.09952655 Eh 
Total entropy correction          ...     -0.03087478 Eh    -19.37 kcal/mol
-----------------------------------------------------------------------
Final Gibbs free energy         ...   -209.13040133 Eh
     
For completeness - the Gibbs free energy minus the electronic energy
G-E(el)                           ...      0.04630314 Eh     29.06 kcal/mol

The Final Gibbs free energy value includes the electronic energy and all contribution and corrections to the free-energy ( $E_{e l .}$ and $G_{R R H O}$ ). Now we need to calculate the solvation free-energy corrections with openCOSMO-RS. To do so, we perform two calculations for acetamide, one in cyclohexane and one in water.

In this example, we will use the solvents from the database with the corresponding inputs

!COSMORS(Cyclohexane)

*XYZFILE 0 1 acetamide.xyz

and

!COSMORS(Water)

*XYZFILE 0 1 acetamide.xyz

From these calculations we will obtain the openCOSMO-RS output that shows the final solvation free-energy correction as well as the energy of the solute in gas-phase, the energy of the solute in solution, and that of the solvent in solution:

----------------------------------------------
Single Point Calculation (solute / gas-phase)
----------------------------------------------
Output single point calculation redirected to >cosmors.solute_vac.lastout

FINAL SINGLE POINT ENERGY (Solute-gas-phase)     -209.312701693624

----------------------------------------------
Single Point Calculation (solute / CPCM)
----------------------------------------------
Output single point calculation redirected to >cosmors.solute_cpcm.lastout

FINAL SINGLE POINT ENERGY (Solute-CPCM)     -209.328833397120

----------------------------------------------
Single Point Calculation (solvent / CPCM)
----------------------------------------------
Output single point calculation redirected to >cosmors.solvent_cpcm.lastout

FINAL SINGLE POINT ENERGY (Solvent-CPCM)     -235.952716268645

----------------------
SOLVATION DATA
----------------------
Reference temperature              :                 298.15 K
Free energy of solvation (dGsolv)  :       -0.005754344722 Eh             -3.610907 kcal/mol

For acetamide in water the corresponding output looks like:

----------------------------------------------
Single Point Calculation (solute / gas-phase)
----------------------------------------------
Output single point calculation redirected to >cosmors.solute_vac.lastout

FINAL SINGLE POINT ENERGY (Solute-gas-phase)     -209.312701693624

----------------------------------------------
Single Point Calculation (solute / CPCM)
----------------------------------------------
Output single point calculation redirected to >cosmors.solute_cpcm.lastout

FINAL SINGLE POINT ENERGY (Solute-CPCM)     -209.328833397120

----------------------------------------------
Single Point Calculation (solvent / CPCM)
----------------------------------------------
Output single point calculation redirected to >cosmors.solvent_cpcm.lastout

FINAL SINGLE POINT ENERGY (Solvent-CPCM)      -76.479236610833

----------------------
SOLVATION DATA
----------------------
Reference temperature              :                 298.15 K
Free energy of solvation (dGsolv)  :       -0.015783182256 Eh             -9.904099 kcal/mol

From these calculations we can now calculate the free-energy of the cyclohexane-water-transfer of acetamide ( $Δ G_{c \to w}$ ). As all other contributions cancel out for this specific example, we can simplify the calculation as the difference of the solvation free-energy corrections:

Δ G_{c \to w} = δ G_{s o l v ., w a t e r} - δ G_{s o l v ., c y c l o h e x a n e} = - 6.29 k c a l / m o l

The result is in excellent agreement with the experimental value of -6.64 kcal/mol.

Structures Example 2#

Available Solvents#

List of available solvents for the different implicit solvation methods in ORCA. For more details, see the ORCA manual.#
Solvent	CPCM	+ DRACO	SMD	+ DRACO	COSMO-RS
1,1,1-trichloroethane	✓		✓
1,1,2-trichloroethane	✓		✓
1,2,4-trimethylbenzene	✓		✓
1,2-dibromoethane	✓		✓		✓
1,2-dichloroethane	✓		✓		✓
1,2-ethanediol	✓		✓
1,4-dioxane / dioxane	✓		✓		✓
1-bromo-2-methylpropane	✓		✓
1-bromooctane / bromooctane	✓		✓		✓
1-bromopentane	✓		✓
1-bromopropane	✓		✓
1-butanol / butanol	✓		✓		✓
1-chlorohexane / chlorohexane	✓		✓		✓
1-chloropentane	✓		✓
1-chloropropane	✓		✓
1-decanol / decanol	✓		✓		✓
1-fluorooctane	✓		✓		✓
1-heptanol / heptanol	✓		✓		✓
1-hexanol / hexanol	✓		✓		✓
1-hexene	✓		✓
1-hexyne	✓		✓
1-iodobutane	✓		✓
1-iodohexadecane / hexadecyliodide	✓		✓		✓
1-iodopentane	✓		✓
1-iodopropane	✓		✓
1-nitropropane	✓		✓
1-nonanol / nonanol	✓		✓		✓
1-octanol / octanol	✓		✓		✓
1-pentanol / pentanol	✓		✓		✓
1-pentene	✓		✓
1-propanol / propanol	✓		✓		✓
2,2,2-trifluoroethanol	✓		✓
2,2,4-trimethylpentane / isooctane	✓		✓		✓
2,4-dimethylpentane	✓		✓
2,4-dimethylpyridine	✓		✓
2,6-dimethylpyridine	✓		✓		✓
2-bromopropane	✓		✓
2-butanol / secbutanol	✓		✓		✓
2-chlorobutane	✓		✓
2-heptanone	✓		✓
2-hexanone	✓		✓
2-methoxyethanol / methoxyethanol	✓		✓		✓
2-methyl-1-propanol / isobutanol	✓		✓		✓
2-methyl-2-propanol	✓		✓
2-methylpentane	✓		✓
2-methylpyridine / 2methylpyridine	✓		✓		✓
2-nitropropane	✓		✓
2-octanone	✓		✓
2-pentanone	✓		✓
2-propanol / isopropanol	✓		✓		✓
2-propen-1-ol	✓		✓
e-2-pentene	✓		✓
3-methylpyridine	✓		✓
3-pentanone	✓		✓
4-heptanone	✓		✓
4-methyl-2-pentanone / 4methyl2pentanone	✓		✓		✓
4-methylpyridine	✓		✓
5-nonanone	✓		✓
acetic acid / aceticacid	✓		✓		✓
acetone	✓		✓		✓
acetonitrile / mecn / ch3cn	✓	✓	✓	✓	✓
acetophenone	✓		✓		✓
ammonia	✓				✓
aniline	✓		✓		✓
anisole	✓		✓		✓
benzaldehyde	✓		✓		✓
benzene	✓		✓		✓
benzonitrile	✓		✓		✓
benzyl alcohol / benzylalcohol	✓		✓		✓
bromobenzene	✓		✓		✓
bromoethane	✓		✓		✓
bromoform	✓		✓		✓
butanal	✓		✓
butanoic acid	✓		✓
butanone	✓		✓		✓
butanonitrile	✓		✓
butyl ethanoate / butyl acetate / butylacetate	✓		✓		✓
butylamine	✓		✓
n-butylbenzene / butylbenzene	✓		✓		✓
sec-butylbenzene / secbutylbenzene	✓		✓		✓
tert-butylbenzene / tbutylbenzene	✓		✓		✓
carbon disulfide / carbondisulfide / cs2	✓		✓		✓
carbon tetrachloride / ccl4	✓		✓		✓
chlorobenzene	✓		✓		✓
chloroform / chcl3	✓		✓		✓
a-chlorotoluene	✓		✓
o-chlorotoluene	✓		✓
conductor	✓
m-cresol / mcresol	✓		✓		✓
o-cresol	✓		✓
cyclohexane	✓		✓		✓
cyclohexanone	✓		✓		✓
cyclopentane	✓		✓
cyclopentanol	✓		✓
cyclopentanone	✓		✓
decalin	✓		✓		✓
cis-decalin	✓		✓
n-decane / decane	✓		✓		✓
dibromomethane	✓		✓
dibutylether	✓		✓		✓
o-dichlorobenzene / odichlorobenzene	✓		✓		✓
e-1,2-dichloroethene	✓		✓
z-1,2-dichloroethene	✓		✓
dichloromethane / ch2cl2 / dcm	✓		✓		✓
diethyl ether / diethylether	✓		✓		✓
diethyl sulfide	✓		✓
diethylamine	✓		✓
diiodomethane	✓		✓
diisopropyl ether / diisopropylether	✓		✓		✓
cis-1,2-dimethylcyclohexane	✓		✓
dimethyl disulfide	✓		✓
n,n-dimethylacetamide / dimethylacetamide	✓		✓		✓
n,n-dimethylformamide / dimethylformamide / dmf	✓		✓		✓
dimethylsulfoxide / dmso	✓	✓	✓	✓	✓
diphenylether	✓		✓		✓
dipropylamine	✓		✓
n-dodecane / dodecane	✓		✓		✓
ethanethiol	✓		✓
ethanol	✓		✓		✓
ethyl acetate / ethylacetate / ethanoate	✓		✓		✓
ethyl methanoate	✓		✓
ethyl phenyl ether / ethoxybenzene	✓		✓		✓
ethylbenzene	✓		✓		✓
fluorobenzene	✓		✓		✓
formamide	✓		✓
formic acid	✓		✓
furan / furane					✓
n-heptane / heptane	✓		✓		✓
n-hexadecane / hexadecane	✓		✓		✓
n-hexane / hexane	✓		✓		✓
hexanoic acid	✓		✓
iodobenzene	✓		✓		✓
iodoethane	✓		✓
iodomethane	✓		✓
isopropylbenzene	✓		✓		✓
p-isopropyltoluene / isopropyltoluene	✓		✓
mesitylene	✓		✓		✓
methanol	✓	✓	✓	✓	✓
methyl benzoate	✓		✓
methyl butanoate	✓		✓
methyl ethanoate	✓		✓
methyl methanoate	✓		✓
methyl propanoate	✓		✓
n-methylaniline	✓		✓
methylcyclohexane	✓		✓
n-methylformamide / methylformamide	✓		✓		✓
nitrobenzene / phno2	✓		✓		✓
nitroethane	✓		✓		✓
nitromethane / meno2	✓		✓		✓
o-nitrotoluene / onitrotoluene	✓		✓
n-nonane / nonane	✓		✓		✓
n-octane / octane	✓		✓		✓
n-pentadecane / pentadecane	✓		✓		✓
octanol(wet) / wetoctanol / woctanol
pentanal	✓		✓
n-pentane / pentane	✓		✓		✓
pentanoic acid	✓		✓
pentyl ethanoate	✓		✓
pentylamine	✓		✓
perfluorobenzene / hexafluorobenzene	✓		✓		✓
phenol	✓				✓
propanal	✓		✓
propanoic acid	✓		✓
propanonitrile	✓		✓
propyl ethanoate	✓		✓
propylamine	✓		✓
pyridine	✓		✓		✓
tetrachloroethene / c2cl4	✓		✓		✓
tetrahydrofuran / thf	✓		✓		✓
tetrahydrothiophene-s,s-dioxide /	✓		✓
/ tetrahydrothiophenedioxide / sulfolane	✓		✓
tetralin	✓		✓		✓
thiophene	✓		✓
thiophenol	✓		✓
toluene	✓		✓		✓
trans-decalin	✓		✓
tributylphosphate	✓		✓		✓
trichloroethene	✓		✓
triethylamine	✓		✓		✓
n-undecane / undecane	✓		✓		✓
water / h2o	✓	✓	✓	✓	✓
xylene	✓		✓
m-xylene	✓		✓
o-xylene	✓		✓
p-xylene	✓		✓

Selected Dielectric Constants#

List of dielectric constants and refractive indices for selected solvents. For more details, see the ORCA manual.#
Solvent	Dielec. Const.	Refrac. Index
Water	80.4	1.33
Acetone	20.7	1.359
Acetonitrile	36.6	1.344
Ammonia	22.4	1.33
Benzene	2.28	1.501
CCl4	2.24	1.466
CH2Cl2	9.08	1.424
Chloroform	4.9	1.45
Cyclohexane	2.02	1.425
DMF	38.3	1.430
DMSO	47.2	1.479
Ethanol	24.3	1.361
Hexane	1.89	1.375
Methanol	32.63	1.329
Octanol	10.3	1.421
Pyridine	12.5	1.510
THF	7.25	1.407
Toluene	2.4	1.497

Implicit Solvation Models#隐式溶剂模型

Overview# 概述

Transition from Gas to Liquid phase#气相到液相的转变

Conductor-like Polarizable Continuum Model (CPCM)#导体类极化连续介质模型 (CPCM)

CPCM and COSMO#

Combining DFT with post-HF methods#

Gaussian point charges#

Universal Solvation Model (SMD)#

Dynamic Radii Adjustment for Continuum Solvation (DRACO)#

Example 1: Octanol/water partition coefficient#

Structures Example 1#

openCOSMO-RS#

Example 2: Cyclohexane to water transfer of acetamide#

Structures Example 2#

Available Solvents#

Selected Dielectric Constants#

Implicit Solvation Models#
隐式溶剂模型

Transition from Gas to Liquid phase#
气相到液相的转变

Conductor-like Polarizable Continuum Model (CPCM)#
导体类极化连续介质模型 (CPCM)