Hi

I am optimizing a dimer system with SF-TDDFT. I ran a job for that keeping one monomer fix:

$molecule

0 3

coordinates

$end

$rem

BASIS = cc-pVDZ

EXCHANGE = omegaB97XD

JOB_TYPE = optimization

sts_mom = true

SCF_CONVERGENCE = 8

MAX_SCF_CYCLES = 700

MAX_CIS_CYCLES = 700

UNRESTRICTED = true

SPIN_FLIP = 1

CIS_N_ROOTS = 4

THRESH = 14

SYMMETRY_IGNORE = true

SYMMETRY = false

CIS_STATE_DERIVATIVE = 1

SOLVENT_METHOD = PCM

geom_opt_max_cycles = 100

$end

$solvent

DIELECTRIC 32.613000

OPTICALDIELECTRIC 1.765709

$end

$opt

FIXED

1:36 XYZ

ENDFIXED

$end

In 100 optimization cycles criteria were not converged so I took the last cycle coordinates and put a job with the same keywords again but I faced the issue with the values.

In the last optimization cycle (100), the situation was this:

```
SF-DFT Excitation Energies
```

## (The first “excited” state might be the ground state)

Excited state 1: excitation energy (eV) = -2.1398

Total energy for state 1: -1797.97035658 au

<S**2> : 0.0535

S( 2) → S( 1) amplitude = 0.9887 alpha

Excited state 2: excitation energy (eV) = 0.4743

Total energy for state 2: -1797.87429054 au

<S**2> : 2.0103

D( 139) → S( 1) amplitude = -0.6612

S( 2) → V( 1) amplitude = 0.7321 alpha

Excited state 3: excitation energy (eV) = 1.5510

Total energy for state 3: -1797.83472418 au

<S**2> : 0.1472

D( 139) → S( 1) amplitude = 0.6878

S( 2) → V( 1) amplitude = 0.6398 alpha

Excited state 4: excitation energy (eV) = 2.0505

Total energy for state 4: -1797.81636797 au

<S**2> : 1.0668

D( 135) → S( 1) amplitude = -0.4719

S( 2) → V( 2) amplitude = -0.2218 alpha

S( 2) → V( 3) amplitude = 0.8262 alpha

But in the second time optimization (I took the last cycle coordinates i.e., 100th optimized cycle coordinates) the situation of excited states is this:

```
SF-DFT Excitation Energies
```

## (The first “excited” state might be the ground state)

Excited state 1: excitation energy (eV) = -1.3635

Total energy for state 1: -1797.90126864 au

<S**2> : 0.1736

S( 2) → S( 1) amplitude = 0.9917 alpha

Excited state 2: excitation energy (eV) = 0.4626

Total energy for state 2: -1797.83416326 au

<S**2> : 1.1583

S( 2) → V( 2) amplitude = 0.9561 alpha

S( 2) → V( 3) amplitude = 0.1820 alpha

Excited state 3: excitation energy (eV) = 0.7540

Total energy for state 3: -1797.82345211 au

<S**2> : 1.2327

D( 136) → S( 1) amplitude = -0.9457

Excited state 4: excitation energy (eV) = 1.1579

Total energy for state 4: -1797.80860917 au

<S**2> : 1.0686

S( 2) → S( 2) amplitude = 0.9805 alpha

What should I have to do to resolve this issue?