# Specification of curves and couplings (Duo objects)¶

Once the main global parameters have been specified as described in the previous sections, it is necessary to introduce the PECs and the various coupling
curves defining the Hamiltonian. Dipole moment curves (DMCs), which are necessary for calculating spectral line intensities, are also discussed in this section, as well as some special objects which are used for fitting. Each object specification consists in a first part in which
keywords are given and a second one (starting from the `values`

keyword) in which numerical values are given;
the order of the keywords is not important, except for `values`

. Each object specification is terminated by the `end`

keyword.

Objects of type `poten`

(i.e., PECs, discussed in more detail below) begin with a line of the kind `poten N`

where N is an integer index number counting over potentials and identifying them. It is recommended that PECs are numbered progressively as 1,2,3,…, although this only restriction is that the total number Nmax of PECs should be not less than the total number of states specified by the keywork `nstates`

.

Most other objects (e.g., `spin-orbit`

) are assumed to be matrix elements of some operator between electronic wave functions and after the keyword identifying their type require two integer numbers specifying the two indexes of the two electronic states involved (bra and ket). The indexes are the numbers specified after the texttt{poten} keyword.

Currently Duo supports the following types of objects: `potential`

, `spinorbit`

, `L2`

, `Lx`

, `spinspin`

, `spinspino`

, `bobrot`

,
`spinrot`

, `diabatic`

, `lambdaopq`

, `lambdap2q`

, `lambdaq`

, `abinitio`

, `brot`

, `dipoletm`

, `nac`

.

`potential`

¶

Alias: `poten`

. Objects of type `poten`

represent potential energy curves (PECs) and are the most fundamental objects underlying each calculation. From the point of view of theory each PEC is the solution of the electronic Schoedinger equation with clamped nuclei, possibly complemented with the scalar-relativistic correction and with the Born-Oppenheimer Diagonal correction (also known as adiabatic correction). Approximate PECs can be obtained with well-known quantum chemistry methods such as Hartree-Fock, coupled cluster theory etc.

Objects of type `poten`

or `potential`

should always appear before all other objects as they are used to assign to each electronic states its quantum numbers. Here is an example for a PEC showing the general structure:

```
poten 1
name "a 3Piu"
symmetry u
type EMO
lambda 1
mult 3
values
V0 0.82956283449835E+03
RE 0.13544137530870E+01
DE 0.50061051451709E+05
RREF -0.10000000000000E+01
PL 0.40000000000000E+01
PR 0.40000000000000E+01
NL 0.20000000000000E+01
NR 0.20000000000000E+01
B0 0.20320375686486E+01
B1 -0.92543284427290E-02
B2 0.00000000000000E+00
end
```

Here `poten 1`

refers to the electronic state 1. This label 1 should be used consistently in all couplings as well as in the description of the experimental data.

From 2023, the state labels can be any string of characters, e.g.

```
poten Ap
name "Ap2Delta"
lambda 2
mult 2
type EMO
values
V0 1.47069212003828e+04 fit ( 1.47070955806154e+04)
RE 1.817000000000000000
DE 5.92200000000000E+04
RREF -1.00000000000000E+00
PL 4.00000000000000E+00
PR 4.00000000000000E+00
NL 1.00000000000000E+00
NR 4.00000000000000E+00
B0 1.700000000000000000
B1 0.000000000000000000
B2 0.000000000000000000
B3 0.000000000000000000
B4 0.000000000000000000
end
```

Integers 1,2,3 from before 2023 will continue working.

`L2`

¶

Alias: `L**2`

. These objects represent matrix elements between electronic states of the molecule-fixed angular momentum operator .

`Lx`

and `L+`

¶

Aliases: `Lplus`

, `LxLy`

and `L+`

. It represent matrix elements between electronic states of the molecule-fixed angular momentum operator and in the - and Cartesian-representations, respectively.

`spin-orbit`

and `spin-orbit-x`

¶

These objects are matrix elements of the Breit-Pauli spin-orbit Hamiltonian in the - and Cartesian-representations, respectively.

Example:

```
spin-orbit 1 3
name "<0,S=0 (X1Sigma+)|LSY|+1 (a3Pi),S=1> SO1"
spin 0.0 1.0
lambda 0 -1
sigma 0.0 -1.0
type grid
factor sqrt(2) (1 or i)
units bohr cm-1
values
2.80 17.500000
2.90 15.159900
3.00 12.347700
3.10 9.050780
3.20 5.391190
3.30 1.256660
3.40 -3.304040
3.50 -8.104950
3.60 -12.848400
3.70 -17.229100
3.80 -21.049000
3.90 -24.250400
4.00 -26.876900
4.10 -29.014700
4.20 -30.756100
4.30 -32.181900
4.50 -34.335500
5.00 -37.348300
end
```

Here 1 and 3 refer to the electronic states `1`

and `3`

as introduced using the corresponding `potential`

:

```
potential 1
name . . .
. . .
end
and
potential 3
. . . . . .
end
```

From 2023, for the electromic states can be labelled using strings of characters, e.g.

```
spin-orbit-x A A
name "<A2Pi|LSZ|A2Pi>"
spin 0.5 0.5
lambda 1 1
sigma 0.5 0.5
units cm-1
factor -i (0, 1 or i)
type polynom_decay_24
<x|Lz|y> -i -i
values
RE 1.79280000000000E+00
BETA 8.00000000000000E-01
GAMMA 2.00000000000000E-02
P 6.00000000000000E+00
B0 2.06176847388046e+02
B1 -7.04066795005532e+01
B2 0.000000000000000000
B3 0.00000000000000E+00
BINF 220.0
end
```

where A is the reference label used for the electronic state `A2Pi`

.

For the `spin-orbit-x`

case (-representation), the value of the matrix elements of the operator must be specified using the `<x|Lz|y>`

keyword. This representation is designed to work with e.g., the MOLPRO outputs. For , the diagonal SO-matrix element (e.g. between to -components of ) should be specified using the component (e.g. ).

`spin-spin`

¶

Parametrised phenomenological spin-spin operator (diagonal and off-diagonal). The diagonal spin-spin matrix elements are given by

.

Note

The definition of is different from the spectroscopic spin-spin constant :

.

The non-diagonal spin-spin matrix elements are given by

where is a reference curve of the projection of spin used to specify the spin-spin field in the Duo input:

and is an off-diagonal spin-spin curve, which is usually reconstructed empirically.

An example of the spin-spin input is given by

```
spin-spin A a
name "<A|SS|a>"
spin 2.5 1.5
factor 1.0
lambda 0 0
sigma 0.5 0.5
type BOBLEROY
values
RE 0.16500000000000E+01
RREF -0.10000000000000E+01
P 0.10000000000000E+01
NT 0.20000000000000E+01
B0 0.74662463783234E-01
B1 0.73073583911575E+01
B2 0.00000000000000E+00
BINF 0.00000000000000E+00
end
```

`spin-rot`

¶

The diagonal matrix elements of the spin-rotational operator are given by

.

The nonzero off-diagonal matrix elements are

.

and

.

`bob-rot`

¶

Alias: `bobrot`

. Specifies the (diagonal) rotational factor (rotational Born-Oppenheimer breakdown term),
which can be interpreted as a position-dependent modification to the rotational mass and is introduced as follows

`diabatic`

¶

Alias: `diabat`

. Non-diagonal coupling of potential energy functions in the diabatic
representation. A diabatic coupling should be centred about the crossing point of the correpsonding diabatic potential curves.
For an analitycal (non-grid) representaion, Duo will automatically finds a crossing between the corresponding
states and store its value to the second parameter of the diabatic field. It is threfore important to reserve the second
line for the reference, expansion point. The search of the crossing point is done by the dividing-by-half approach until the
convergence (or 100 iterations) is reached. Only one crossing is currenly supported.

Example:

```
diabatic B D
name "<B2Sigma+|DC|D2Sigma+>"
lambda 0 0
spin 0.5 0.5
type Lorentz
factor 1.0
values
V0 0.000000000000000000
RE 2.08 (this value will be replaced by the actual crossing point between B and D)
gamma 1.99627265568284e-01
a 2.75756224068962e+02
f1 0.000000000000000000
end
```

## Non-adiabatic coupling: `NAC`

¶

Non-adiabatic coupling (NAC). It is a non-diagonal coupling element used for adiabatic representation. It appears in the kinetic energy operator as a linear momentum term:

,

where 12 stands for the coupling between states 1 and 2. By default, a NAC field trigers the “second order NAC” corrections to the corresponding potential energies defined as

where . In Duo, the diagonal `diabatic`

fields are used to store . If however, the corresponding diabatic fields are
directly specified, these second order NAC correction are ignored.

A typical NAC is a Lorentz- or Gaussian-type functions. NAC should be centred about the crossing point of the correpsonding diabatic potential curves.

Example:

```
NAC B D
name "<B2Sigma+|NAC|D2Sigma+>"
lambda 0 0
spin 0.5 0.5
type Lorentz
factor 1.0
values
V0 0.000000000000000000
RE 2.08 (this value will be replaced by the actual crossing point between B and D)
gamma 1.99627265568284e-01
a 1.0
f1 0.000000000000000000
end
```

The second order NAC corrections can be provided as two diagonal diabatic fields, e.g. (from the YO spectroscopic model)

Example:

```
diabatic B B
name "<B2Sigma+|NAC2|B2Sigma+>"
lambda 0 0
spin 0.5 0.5
type grid
factor 1.243548973
values
1.81020 0.0731621425
1.81040 0.0735930439
1.81060 0.0740271189
1.81080 0.0744643954
1.81100 0.0749049019
1.81120 0.0753486669
1.81140 0.0757957194
1.81160 0.0762460887
1.81180 0.0766998042
1.81200 0.0771568959
1.81220 0.0776173938
1.81240 0.0780813285
1.81260 0.0785487308
1.81280 0.0790196317
end
```

```
diabatic D D
name "<D2Sigma+|NAC2|D2Sigma+>"
lambda 0 0
spin 0.5 0.5
type grid
factor 1.243548973
values
1.81020 0.0731621425
1.81040 0.0735930439
1.81060 0.0740271189
1.81080 0.0744643954
1.81100 0.0749049019
1.81120 0.0753486669
1.81140 0.0757957194
1.81160 0.0762460887
1.81180 0.0766998042
1.81200 0.0771568959
1.81220 0.0776173938
1.81240 0.0780813285
1.81260 0.0785487308
1.81280 0.0790196317
end
```

Here `factor 1.243548973`

is for YO.

`lambda-opq`

, `lambda-p2q`

, and `lambda-q`

¶

- These objects are three Lambda-doubling objects which correspond to
, , and couplings.

Example:

```
lambda-p2q 1 1
name "<X,2Pi|lambda-p2q|X,2Pi>"
lambda 1 1
spin 0.5 0.5
type BOBLEROY
factor 1.0
values
RE 0.16200000000000E+01
RREF -0.10000000000000E+01
P 0.10000000000000E+01
NT 0.20000000000000E+01
B0 0.98500969657331E-01
B1 0.00000000000000E+00
B2 0.00000000000000E+00
BINF 0.00000000000000E+00
end
```

`abinitio`

¶

Objects of type `abinitio`

(aliases: `reference`

, `anchor`

) are reference, `abinitio`

curves which may be specified during fitting. When they are used they constrain the fit so that the fitted function differs as little as possible from the ab initio (reference). The reference curve is typically obtained by ab initio methods. For any Duo object one can specify a corresponding reference curve as in the following example:

```
abinitio spin-orbit 1 2
name "<3.1,S=0,0 (B1pSigma)|LSX|+1 (d3Pig),S=1,1>"
spin 0.0 1.0
type grid
units bohr cm-1
values
2.3 -3.207178925 13.0
2.4 -3.668814404 24.0
2.5 -4.010985122 35.0
2.6 -4.271163495 46.0
2.7 -4.445721312 47.0
2.8 -4.468083270 48.0
end
```

`dipole`

and `dipole-x`

¶

`Dipole`

(aliases: `dipole-moment`

, `TM`

): Diagonal or transition dipole moment curves (DMCs), necessary for computing (dipole-allowed) transition line intensities and related quantities (Einstein coefficients etc.).

`dipole-x`

is related to the Cartesian-representation.

At the moment Duo cannot compute magnetic dipole transition line intensities.

`quadrupole`

¶

The keyword `quadrupole`

is used to specify transition quadrupole moment curves, which are necessary for computing electric-quadrupole transition line intensities and related quantities. The actual calculation of line strengths requires the `quadrupole`

keyword in the `intensity`

section also (see here).

The quadrupole moment is defined in Cartesian coordinates by the following expression the Shortley convention:

where is the charge of the electron with position vector . This differs from the Buckingham convention, which is used in many quantum chemistry programs, where:

Currently Duo requires quadrupole moment curves to be provided in the spherical irreducible representation, with atomic units (a.u.), which can be obtain from the Cartesian components in the Buckingham convention via the relations given by Eq. (6) - (11) of W. Somogyi et al., JCP 155, (2021).

Additionally, the units must be specified via the `units`

keyword. For example

```
quadrupole 1 1
name "<X3Sigma-|QM20|X3Sigma->"
spin 1 1
lambda 0 0
type grid
units angstrom au
values
0.8 -1.4747
0.9 -1.1434
...
end
```

## Keywords used in the specification of objects¶

### Name and quantum numbers¶

This is a list of keywords used to specify various parameters of Duo objects.

`name`

: object name.

`name`

is a text label which can be assigned to any object for reference in the output. The string must appear within quotation marks.
Examples:

```
name "X 1Sigma+"
name "<X1Sigma\|HSO\|A3Pi>"
```

`lambda`

: The quantum number(s) .

`Lambda`

specifies the quantum number(s) , i.e. projections of the electronic angular momentum onto the molecular axis, either for one (PECs) or two states (couplings). It must be an integral number and is allowed to be either positive or negative. The sign of is relevant when specifying couplings between degenerate states in the spherical representation (e.g. `spin-orbit`

)
Examples:

```
lambda 1
lambda 0 -1
```

The last example is relative to a coupling-type object and the two numbers refer to the bra and ket states.

`sigma`

: Spin-projection.

`sigma`

specifies the quantum number(s) , i.e. the projections of the total spin onto the molecular axis, either for one (diagonal) or two states (couplings). These values should be real () and can be half-integral, where is the total spin. `sigma`

is currently required for the spin-orbit couplings only.

Example:

```
sigma 0.5 1.5
```

where two numbers refer to the bra and ket states.

`mult`

(alias:`multiplicity`

): Multiplicity

`mult`

specifies the multiplicity of the electronic state(s), given by , where is the total spin. It must be an integer number and is an alternative to the `spin`

keyword.

Examples:

```
mult 3
mult 1 3
```

The last example is relative to a coupling-type object and the two numbers refer to the bra and ket states.

`spin`

: Total spin.

The total `spin`

of the electronic state(s), an integer or half-integer number.
Example:

```
spin 1.0
spin 0.5 1.5
```

The last example is relative to a coupling-type object and the two numbers refer to the bra and ket states.

`symmetry`

: State symmetry

This keyword tells Duo if the electronic state has gerade `g`

or ungerade `u`

symmetry (only for homonuclear diatomics) and whether it has positive (`+`

) or negative `-`

parity (only for states, i.e. states with , for which it is mandatory).

Examples:

```
symmetry +
```

```
symmetry + u
```

```
symmetry g
```

The keywords `g`

/`u`

or `+`

/`-`

can appear in any order.

### Other control keys¶

`type`

: Type of the functional representaion.

`Type`

defines if the object is given on a grid `type grid`

or selects the parametrised analytical function used for representing the objects or selects the interpolation type to be used. The function types supported by Duo are listed in Duo Functions.

Examples:

```
type grid
type polynomial
type morse
```

In the examples above `grid`

selects numerical interpolation of values given on a grid, `polynomial`

selects a polynomial expansion and `morse`

selects a polynomial expansion in the Morse variable. See Duo Functions for details.

`Interpolationtype`

: Grid interpolation

is used only for `type grid`

and specifies
the method used for the numerical interpolation of the numerical values. The currently implemented interpolation methods are `Cubicsplines`

and `Quinticsplines`

(default).

Example:

```
Interpolationtype Cubicsplines
Interpolationtype Quinticsplines
```

`factor`

: Scaling factor

This optional keyword permits to rescale any object by an arbitrary multiplication factor. At the moment the accepted values are any real number, the imaginary unit , the square root of two, written as `sqrt(2)`

, or products of these quantities. To write a product simply leave a space between the factors, but do not use the `*`

sign. All factor can have a sign. The default value for `factor`

is 1. This keyword is useful, for example, to temporarily zero a certain object without removing it from the input file.

Examples:

```
factor 1.5
factor -sqrt(2)
factor sqrt(2)
factor 5 i
factor -2 sqrt(2) i
```

In the last example the factor is read in as . Note that imaginary factors make sense only in some cases for some coupling terms (in particular, spin-orbit) in the Cartesian-representation, see Section~ref{s:representations}.

`units`

This keyword selects the units of measure used for the the object in question. Supported units are: `angstroms`

(default) and `bohr`

for the bond lengths; `cm-1`

(default), `hartree`

(aliases are `au`

, `a.u.`

, and `Eh`

), and `eV`

(electronvolts) for energies; `debye`

(default) and `ea0`

(i.e., atomic units) for dipoles; units can appear in any order.

Note

Quadrupole moment curves must be provided to Duo in atomic units, so the `units`

keyword is invalid for these objects.

Example:

```
units angstrom cm-1 (default for poten, spin-orbit, lambda-doubling etc)
units bohr cm-1
units debye (default)
units ae0 bohr
```

`<x|Lz|y>`

,`<z|Lz|xy>`

(aliases`<a|Lz|b>`

and`<1|Lz|2>`

)

This keyword is sometimes needed when specifying coupling curves between electronic states with in order to resolve ambiguities in the definition of the degenerate components of each electronic state, see:ref:representations.

This keyword specifies the matrix element of the operator between the degenerate components of the electronic wave function.

Examples:

```
<x|Lz|y> i -i
<z|Lz|xy> -2i i
```

These matrix elements are pure imaginary number in the form . It is the overall sign which Duo needs and cannot be otherwise guessed. As shown in the examples above, each factor should be written in the form without any space or `*`

sign.

`Molpro`

A single, stand-alone keywrd to trigger the molpro even for non-x fields.

Example:

molpro

`morphing`

This keyword is used for fitting and switches on the morphing method.

`ZPE`

: Zero-point-energy

`ZPE`

allows to explicitly input the zero-point energy (ZPE) of the molecule (in cm^{-1}). This affects the value printed, as by default Duo prints energy of rovibronic levels by subtracting the ZPE. If not specified, the lowest energy of the first -block (independent of parity) will be used as appear on the line `Jlist`

.

`fit_factor`

This factor () is used as a part of the reference *ab initio* curves of the `abinitio`

type which (when given) is applied to the corresponding weights assigned to the corresponding values of this object. It is different from `fit_factor`

defined within in Duo Fitting.

`adjust`

This keyword can be used to add a constant value to the values of the potential, which is useful e.g when there is a known systematic error in the values. The keyword is followed by a value and (optionally) units. For a list of the available units see the `units`

keyword above. Note that the units of the shift can be different to the units specified using the `units`

keyword. Default units are `cm-1`

for PECs, `debye`

for dipole moment curves, and `au`

(atomic units) for quadrupole moment curves.

Examples:

```
adjust -42 cm-1
```

```
::
```

adjust

Example:

```
abinitio poten 1
name "A 1Pi"
type grid
lambda 1
mult 1
units bohr cm-1
fit_factor 1e1
values
2.00 32841.37010 0.01
2.20 17837.88960 0.10
2.40 8785.33147 0.70
2.60 3648.35520 1.00
2.70 2107.10737 1.00
2.80 1073.95670 1.00
2.90 442.52180 1.00
3.00 114.94960 1.00
3.10 0.00000 1.00
3.20 48.46120 1.00
3.30 213.34240 1.00
3.40 455.16980 1.00
3.50 739.61170 1.00
3.60 1038.82620 1.00
3.70 1332.46170 1.00
4.00 2059.31119 1.00
4.50 2619.19233 0.30
5.00 2682.84741 0.30
6.00 2554.34992 0.30
8.00 2524.31106 0.30
10.00 2561.48269 1.00
12.00 2575.09861 1.00
end
```

### Definition of the function or a grid¶

`values`

This keyword starts the subsection containing the numerical values defining the object. For one of the ```
type``s corresponding to an analytic function,
the input between ``values
```

and `end`

contains the values of the parameters of the function. The input consists in two columns separated by spaces containing (i) a string label identifying the parameter and (ii) the value of the parameter (a real number).

In case of `fitting`

(see Duo Fitting) a third column should also be provided; the parameters which are permitted to vary during fitting
must have in the third column the string `fit`

or, alternatively, the letter `f`

or the number 1. Any other string or number (for example, the string `nofit`

or the number 0) implies the parameter should be kept at its initial value. In the case of fitting, the keyword `link`

can be also appear at the end of each the line; this keyword permits to cross-reference values from different objects and is explained
below in this section.

In the case of objects of type `grid`

, the third column can be also used to specify if the grid point needs to vary. The first columns contains the bond length and a second with the value of the object. In the case of object of the `abinitio`

(`reference`

) type and specified as `grid`

a third column can be used to specify the fitting weights (see Duo Fitting).

`link`

This special keyword is used in fitting to force a set of parameters (which may be relative to a different object) to have the same value. For example, in a typical situation one may want to fit a set of PECs and to constrain their dissociation (asymptotic) energy to the same value (because they are expected from theory to share the same dissociation channel).

After the keyword `link`

one should provide three numbers , , defining the parameter ID, where identifies the object type (e.g. `poten`

, `spin-orbit`

, `spin-rot`

etc.), is the object number within the type and is the parameter number as it appears after `values`

. The ID numbers are specified in the fitting outputs in the form [i,j,k].

Example of the input:

```
DE 0.50960000000000E+05 fit link 1 1 3
```

Example of the corresponding output

```
DE 0.50960000000000E+05 [ 1 1 3 ]
```

### Using ab initio couplings in Duo: Representations of the electronic wave functions¶

Quantum chemistry programs generally use real-valued electronic wave functions which transform according to the irreducible representations of the C:sub:2v point group (for heteronuclear diatomics) or of D:math:2h (for homonuclear diatomics). On the other hand Duo internally assumes the electronic wave functions are eigenfunctions of the operator, which implies they must be complex valued for . Converting from one representation to the other is simple, as

where and are two Cartesian components of the electronic wave functions in a quantum chemistry program. Duo uses the matrix elements of the to reconstruct the transformation between two representations:

The keyword `<x|Lz|y>`

and `<z|Lz|xy>`

(aliases `<a|Lz|b>`

and `<1|Lz|2>`

) is required when specifying coupling curves between electronic states in the `MOLPRO`

representation (`spin-orbit-x`

, `Lx`

and `dipole-x`

) with in order to resolve ambiguities in the definition of the degenerate components of each electronic state. This is also the value of the matrix element of the operator computed for the two component spherical harmonic, degenerate functions and for the states or and for the states etc. The corresponding <x|Lz|y> values for both coupled states must be provided.

Examples:

```
<x|Lz|y> i -i
```

```
<z|Lz|xy> -2i i
```

This keyword is required for the couplings of the following types: `spin-orbit-x`

, `Lx`

and `dipole-x`

. The suffix `-x`

indicates that Duo expects the `x`

-component (non-zero) of the corresponding coupling.

This keyword should appear anywhere in the object section, before the `values`

keyword.

```
spin-orbit-x 1 1
name "X-X SO term"
spin 1.0 1.0
lambda 2 2
sigma 1.0 1.0
units angstrom cm-1
type polynomial
factor i
<x|Lz|y> 2i 2i
values
f 101.2157
end
```

These matrix elements are pure imaginary number in the form . It is the overall sign which Duoneeds and cannot be otherwise guessed. As shown in the examples above, each factor should be written in the form without any space or * sign.