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SUGGESTED CAMERA AND FLASH SETTINGS
INDOORS - SHOOT WITH FLASH ON TTL MODE
SET CAMERA ON EITHER MANUAL OR APERTURE PRIORITY
SLOW DOWN THE SHUTTER AND OPEN UP THE APERTURE!
Put your camera flash on E-TTL and set your camera on either Aperture Priority or Manual Mode so you can control both the shutter speed and the aperture.
An open aperture blurs the backgrounds for a very soft and flattering look. It also saves your battery from drain, as each stop that you open will cut your recycle time and battery usage in half.
Note how dark the background is for the image on the right. It also took three times more battery power because there is a four stop difference between f5.6 and f1.4. Shooting at closed apertures will increase your recycle time, darken your backgrounds, and drain your flash batteries.
For wedding receptions, I usually set my camera at 1/45 sec at f2.8, (via Manual Mode) either in ISO 400 or 800. I set the flash on E-TTL. Here's an example:

OUTDOORS - SHOOT WITH FLASH ON E-TTL MODE
SET CAMERA ON PROGRAM MODE
SET CAMERA ON LOWEST ISO SETTING (80-100)
Your camera can only offer a shutter speed of about 1/200 of a second with flash outdoors. On bright days, this will force your camera to select a small aperture (like f8) to compensate. The lower your ISO, the more you can open up the f stops.

Having a more wide-open fstop means your flash can generate less power to light up your subject. In other words, choosing a low ISO will basically make your backgrounds more dark, in relation to the flash.
Shooting closeup, you can use the Lightsphere with internal dome straight up outdoors. At further distances you will want to aim the Lightsphere forward with the dome attached.
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 Introduction  Mounting  Settings  Indoors  High Ceilings  Outdoors  Gary's Blog  Reference Card